US5206104A - Electrophotographic light-sensitive material - Google Patents
Electrophotographic light-sensitive material Download PDFInfo
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- US5206104A US5206104A US07/655,608 US65560891A US5206104A US 5206104 A US5206104 A US 5206104A US 65560891 A US65560891 A US 65560891A US 5206104 A US5206104 A US 5206104A
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/02—Charge-receiving layers
- G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
- G03G5/05—Organic bonding materials; Methods for coating a substrate with a photoconductive layer; Inert supplements for use in photoconductive layers
- G03G5/0528—Macromolecular bonding materials
- G03G5/0592—Macromolecular compounds characterised by their structure or by their chemical properties, e.g. block polymers, reticulated polymers, molecular weight, acidity
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/02—Charge-receiving layers
- G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
- G03G5/05—Organic bonding materials; Methods for coating a substrate with a photoconductive layer; Inert supplements for use in photoconductive layers
- G03G5/0528—Macromolecular bonding materials
- G03G5/0589—Macromolecular compounds characterised by specific side-chain substituents or end groups
Definitions
- the present invention relates to an electrophotographic light-sensitive material, and more particularly to an electrophotographic light-sensitive material which is excellent in electrostatic characteristics, moisture resistance and durability.
- An electrophotographic light-sensitive material may have various structures depending upon the characteristics required or an electrophotographic process to be employed.
- An electrophotographic system in which the light-sensitive material comprises a support having thereon at least one photoconductive layer and, if necessary, an insulating layer on the surface thereof is widely employed.
- the electrophotographic light-sensitive material comprising a support and at least one photoconductive layer formed thereon is used for the image formation by an ordinary electrophotographic process including electrostatic charging, imagewise exposure, development, and, if desired, transfer.
- Binders which are used for forming the photoconductive layer of an electrophotographic light-sensitive material are required to be excellent in the film-forming properties by themselves and the capability of dispersing photoconductive powder therein. Also, the photoconductive layer formed using the binder is required to have satisfactory adhesion to a base material or support. Further, the photoconductive layer formed by using the binder is required to have various excellent electrostatic characteristics such as high charging capacity, small dark decay, large light decay, and less fatigue due to prior light-exposure and also have an excellent image forming properties, and the photoconductive layer stably maintains these electrostatic characteristics regardless of change of humidity at the time of image formation.
- binder resins for a photoconductive layer which satisfy both the electrostatic characteristics as an electrophotographic light-sensitive material and printing properties as a printing plate precursor are required.
- binder resins used for electrophotographic light-sensitive materials have various problems particularly in electrostatic characteristics such as a charging property, dark charge retention and photosensitivity, and smoothness of the photoconductive layer.
- binder resins which have been developed for lithographic printing master plate by an electrophotographic system have been found, upon practical evaluations, that they have also problems in the above-described electrostatic characteristics, background staining of prints, etc.
- JP-A-63-217354 and JP-A-1-70761 disclose improvements in the smoothness of the photoconductive layer and electrostatic characteristics by using, as a binder resin, a resin containing from 0.05 to 10% by weight of a copolymer having an acidic group in a side chain of the polymer or a resin having a weight average molecular weight of from 1 ⁇ 10 3 to 1 ⁇ 10 4 and having an acidic group bonded at only one terminal of the polymer main chain thereby obtaining an image having no background stains.
- JP-A-1-100554 and JP-A-1-214865 disclose a technique using, as a binder resin, a resin containing an acidic group in a side chain of the copolymer or at the terminal of the polymer main chain, and containing a polymerizable component having a heat- and/or photo-curable functional group;
- JP-A-1-102573 and JP-A-2-874 disclose a technique using a resin containing an acidic group in a side chain of the copolymer or at the terminal of the polymer main chain, and a crosslinking agent in combination;
- JP-A-64-564, JP-A-63-220149, JP-A-63-220148, JP-A-1-280761, JP-A-1-116643 and JP-A-1-169455 disclose a technique using a resin having a low molecular weight (a weight average molecular weight of from 1 ⁇ 10 3 to 1 ⁇ 10 4 ) and a resin having a high molecular weight (a
- the film strength of the photoconductive layer can be increased sufficiently and also the mechanical strength of the light-sensitive material can be increased without adversely affecting the above-described electrostatic characteristics achieved by using a resin containing an acidic group in a side chain or at the terminal of the polymer main chain.
- the exposure time is longer than the exposure time in a conventional overall simultaneous exposure system by visible light, and also there is a restriction on the intensity of the light exposure. Accordingly, a higher performance is required for electrostatic characteristics, in particular, dark charge retention and light sensitivity.
- the present invention has been made for solving the above-described problems of conventional electrophotographic light-sensitive material.
- An object of the present invention is to provide an electrophotographic light-sensitive material stably maintaining good electrostatic characteristics and giving clear images of good quality even when the environmental conditions during the formation of duplicated images are changed to low temperature and low humidity or to high temperature and high humidity.
- Another object of the present invention is to provide an electrophotographic light-sensitive material for CPC having excellent electrostatic characteristics and showing less dependency on environmental conditions.
- a still another object of the present invention is to provide an electrophotographic light-sensitive material effective for a scanning exposure system using a semiconductor laser beam.
- a further object of the present invention is to provide a lithographic printing master plate having excellent electrostatic characteristics (in particular, dark charge retention and light sensitivity) as a lithographic printing master plate by an electrophotographic system, capable of reproducing faithfully duplicated images to an original, causing neither overall uniform background stains nor dot-like background stains on the prints, having an excellent printing durability, and causing no edge marks of cutting on the prints.
- electrostatic characteristics in particular, dark charge retention and light sensitivity
- an electrophotographic light-sensitive material comprising a support having provided thereon a photoconductive layer containing at least an inorganic photoconductive substance and a binder resin, wherein the binder resin comprises at least one kind of binder resin (A) or (A') and at least one kind of binder resin (B):
- a graft copolymer having a weight average molecular weight of from 1 ⁇ 10 3 to 2 ⁇ 10 4 comprising at least a monofunctional macromonomer (MA) and a monomer represented by formula (III), wherein the monofunctional macromonomer (MA) has a weight average molecular weight of not more than 2 ⁇ 10 4 and has a polymerizable double bond group represented by following formula (I) at only one terminal of the main chain of a polymer containing at least one of the polymer components represented by following formula (IIa) and (IIb), wherein the copolymer has at least one acidic group selected from --PO 3 H 2 , ##STR1## carbon group or --OR' (wherein R' represents a hydrocarbon group)), and a cyclic acid anhydride-containing group bonded to only one terminal of the main chain of the copolymer; ##STR2## wherein A o represents --COO--, --OCO--, --(CH 2 ) l .sbsb
- R 1 represents a hydrogen atom or a hydrocarbon group
- R 1 represents a hydrogen atom or a hydrocarbon group
- R 1 represents a hydrogen atom or a hydrocarbon group
- R 1 represents a hydrogen atom or a hydrocarbon group
- R 1 represents a hydrogen atom or a hydrocarbon group
- R 1 represents a hydrogen atom or a hydrocarbon group
- R 1 represents a hydrogen atom or a hydrocarbon group
- R 1 represents a hydrogen atom or a hydrocarbon group
- a 1 and a 2 which may be the same or different, each represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, --COO--D 1 or --COO--D 1 via a hydrocarbon group (wherein D 1 represents a hydrocarbon group which may be substituted)
- a 1 has the same meaning as A o in formula (I) described above
- B 1 represents an aliphatic group having from 1 to 18 carbon atoms or an aromatic group having
- a copolymer having a weight average molecular weight of from 1 ⁇ 10 3 to 2 ⁇ 10 4 comprising at least a monofunctional macromonomer (MA') and a monomer represented by the above formula (III), wherein the monofunctional macromonomer (MA') has a weight average molecular weight of not more than 2 ⁇ 10 4 and has a polymerizable double bond group represented by the above formula (I) at only one terminal of the main chain of a polymer containing at least one of the polymer components represented by the above formulae (IIa) and (IIb) and a polymer component containing at least one acidic group selected from ##STR8## (wherein R represents a hydrocarbon group or --OR' (wherein R' represents a hydrocarbon group));
- a graft type copolymer having a weight average molecular weight of from 3 ⁇ 10 4 to 1 ⁇ 10 6 containing as a copolymer component at least one kind of a monofunctional macromonomer (M) having a weight average molecular weight of from 1 ⁇ 10 3 to 2 ⁇ 10 4 having a polymerizable double bond group at the terminal of the polymer main chain of a B block of an AB block copolymer composed of an A block containing at least one polymer component containing at least one acidic group selected from ##STR9## (wherein R o has the same meaning as R described above), and a cyclic acid anhydride-containing group and a B block containing at least a polymer component represented by the following formula (IV); ##STR10## wherein d 1 and d 2 each represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, --COO--R 24 or --COO--R 24 via a hydrocarbon group (wherein
- R 23 represents a hydrogen atom or a hydrocarbon group
- R 23 represents a hydrogen atom or a hydrocarbon group
- --CONHCOO-- represents a hydrocarbon group
- --CONHCONH-- or ##STR12##
- R 21 represents a hydrocarbon group, provided that, when X 3 is ##STR13##
- R 21 represents a hydrogen atom or a hydrocarbon group.
- the binder resin used in the present invention contains at least the low molecular weight resin (A) and the high molecular weight resin (B) described above, and, in the second embodiment of the present invention, the binder resin used in the present invention contains at least the low molecular weight resin (A') and the high molecular weight resin (B) described above.
- the binder resin in the first embodiment is composed of at least the low molecular weight resin (A) which is a graft copolymer containing the monofunctional macromonomer (MA) and the monomer (monomer A) represented by formula (III) described above and has the specific acidic group at only one terminal of the main chain of the polymer, and the high molecular weight resin (B) composed of a graft type copolymer containing, as a copolymerizable component, at least one monofunctional macromonomer (M) comprising an AB block copolymer being composed of an A block comprising a polymerizable component containing the specific acidic group described above and a B block comprising a polymerizable component represented by the general formula (IV) described above and having a polymerizable double bond group bonded to the terminal of the main chain of the B block polymer.
- the low molecular weight resin (A) is a low molecular weight resin (hereinafter referred to as resin (A 1 )) having an acidic group bonded to the terminal of the polymer main chain thereof and containing a methacrylate component having a specific substituent containing a benzene ring which has a specific substituent(s) at the 2-position or 2- and 6-positions thereof or a specific substituent containing an unsubstituted naphthalene ring represented by the following general formula (Va) or (Vb): ##STR14## wherein G 1 and G 2 each represents a hydrogen atom, a hydrocarbon group having from 1 to 10 carbon atoms, a chlorine atom, a bromine atom, --COL 1 or --COOL 2 , wherein L 1 and L 2 each represents a hydrocarbon group having from 1 to 10 carbon atoms; and Z 1 and Z 2 each represents a mere bond or a linking group containing from 1 to 4 linking
- the high molecular weight resin (B) is a graft type copolymer containing at least one macromonomer (M) described above and a polymer component represented by the following general formula (VI): ##STR15## wherein d 3 , d 4 , X 4 and R 22 each has the same meaning as defined for d 1 , d 2 , X 3 and R 21 in formula (IV) described above.
- the acidic group bonded to the terminal of the polymer main chain of the resin (A) of a low molecular weight which comprises the specific macromonomer (MA) and the monomer (A) is adsorbed onto stoichiometrical defects of an inorganic photoconductive substance, and the resin has a function to improve covering power for the photoconductive substance due to its low molecular weight, to sufficiently cover the surface thereof, whereby electron traps of the photoconductive substance can be compensated for and humidity resistance can be greatly improved, while assisting the photoconductive substance to be sufficiently dispersed without forming aggregates.
- the resin (B) not only serves to sufficiently heighten the mechanical strength of a photoconductive layer, which may be insufficient in case of using the resin (A) alone, without damaging the excellent electrophotographic characteristics attained by the use of the resin (A), but also provides sufficiently high image forming performance in the case of changing the environmental conditions or in the case of using a laser beam of small power.
- the excellent characteristics of the electrophotographic light-sensitive material can be obtained by employing the resin (A) and the resin (B) as binder resins for inorganic photoconductive substance, wherein the weight average molecular weight of the resins and the content and position of the acidic group therein are specified, whereby the strength of interactions between the inorganic photoconductive substance and the resins can be appropriately controlled.
- the electrophotographic characteristics, particularly, V 10 , DRR and E 1/10 of the electrophotographic material can be furthermore improved as compared with the use of the resin (A). While the reason of this fact is not fully clear, it is believed that the polymer molecular chain of the resin (A 1 ) suitably arranges on the surface of inorganic photoconductive substance such as zinc oxide in the layer depending on the plane effect of the benzene ring having a substituent at the ortho position or the naphthalene ring which is an ester component of the methacrylate whereby the above described improvement is achieved.
- the smoothness of the photoconductive layer is improved.
- an electrophotographic light-sensitive material having a photoconductive layer with a rough surface is used as an electrophotographic lithographic printing plate precursor, the dispersion state of inorganic particles as photoconductive substance and a binder resin is improper and thus a photoconductive layer is formed in a state containing aggregates of the photoconductive substance, whereby the surface of the non-image portions of the photoconductive layer is not uniformly and sufficiently rendered hydrophilic by applying thereto an oil-desensitizing treatment with an oil-desensitizing solution to cause attaching of printing ink at printing, which results in the formation of background stains in the non-image portions of the resulting prints.
- the interaction of adsorption and covering between the inorganic photoconductive substance and the binder resins is suitably performed, and the sufficient mechanical strength of the photoconductive layer is achieved by the combination of the resins described above.
- the weight average molecular weight is suitably from 1 ⁇ 10 3 to 2 ⁇ 10 4 , preferably from 3 ⁇ 10 3 to 1 ⁇ 10 4 .
- the content of the monofunctional macromonomer (MA) having at least one of the polymer components represented by formulae (IIa) and (IIb) described above in the resin (A) is from 3 to 70% by weight, and preferably from 10 to 50% by weight.
- the content of the monomer (A) represented by formula (III) in the resin (A) is from 10 to 95% by weight, and preferably from 30 to 90% by weight.
- the content of the copolymer component of methacrylate corresponding to the repeating unit shown by formula (Va) and/or formula (Vb) in the resin (A 1 ) is from 30 to 97% by weight, and preferably from 50 to 95% by weight, and the content of the above-described acidic group-containing component is from 1 to 20% by weight, and preferably from 2 to 10% by weight per 100 parts by weight of the resin (A).
- the glass transition point of the resin (A) is preferably from -40° C. to 110° C., and more preferably from -20° C. to 90° C.
- the molecular weight of the resin (A) is less than 1 ⁇ 10 3 , the film-forming ability thereof is undesirably reduced, whereby the photoconductive layer formed cannot keep a sufficient film strength, while if the molecular weight thereof is larger than 2 ⁇ 10 4 , the fluctuations of electrophotographic characteristics (in particular, dark decay retention rate and photosensitivity of E 1/10 ) of the photoconductive layer containing a spectral sensitizing dye for the sensitization in the range of from near-infrared to infrared become somewhat large and thus the effect for obtaining stable duplicated images according to the present invention is reduced under severe conditions of high temperature and high humidity or low temperature and low humidity.
- the resulting electrophotographic light-sensitive material has an initial potential too low to provide a sufficient image density. If, on the other hand, it is more than 20% by weight, dispersibility of the photoconductive substance is reduced, the smoothness of the photoconductive layer and the electrophotographic characteristics thereof under a high humidity condition are deteriorated. Further, background stains are increased when it is used as an offset master.
- the content of the copolymer component corresponding to the macromonomer (MA) is less than 5% by weight, the same phenomena as the case that the weight average molecular weight of the resin (A) becomes larger than 2 ⁇ 10 4 occur.
- the content of the copolymer component is more than 80% by weight, the copolymerization with the monomer A is reluctant to sufficiently proceed, the polymer of the monomer of formula (III) only or of other monomers only forms in addition to the desired graft copolymer, which gives undesirable results.
- an inorganic photoconductive substance is dispersed using such a resin, aggregates of the resin with the photoconductive substance are formed.
- the weight average molecular weight of the resin (B) is from 3 ⁇ 10 4 to 1 ⁇ 10 6 , and preferably from 5 ⁇ 10 4 to 5 ⁇ 10 5 .
- the content of the monofunctional macromonomer composed of the AB block copolymer component in the polymer is preferably from 1 to 60% by weight, and more preferably from 5 to 50% by weight. Furthermore, the content of the polymer content shown by formula (V) is preferably from 40 to 99% by weight, and more preferably from 50 to 95% by weight.
- the glass transition point of the resin (B) is preferably from 0° C. to 110° C., and more preferably from 20° C. to 90° C.
- the molecular weight of the resin (B) is less than 3 ⁇ 10 4 , a sufficient film strength may not be maintained.
- the molecular weight thereof is larger than 1 ⁇ 10 6 , the dispersibility of the photoconductive substance is reduced, the smoothness of the photoconductive layer is deteriorated, and image quality of duplicated images (particularly reproducibility of fine lines and letters) is degradated. Further, the background stains are increased in case of using it as an offset master.
- the content of the macromonomer is less than 1% by weight in the resin (B)
- electrophotographic characteristics may be reduced and the fluctuations of electrophotographic characteristics of the photoconductive layer, particularly that containing a spectral sensitizing dye for the sensitization in the range of from near-infrared to infrared become large under severe conditions.
- the reason therefor is considered that the construction of the polymer becomes similar to that of a conventional homopolymer or random copolymer due to the presence of only a small amount of macromonomer portion which constitutes the graft portion.
- the content of the macromonomer in the resin (B) is more than 60% by weight, the copolymerizability of the macromonomer with other monomers corresponding to other copolymerizable components may become insufficient, and the sufficient electrophotographic characteristics can not be obtained as the binder resin.
- the resin (A) of the present invention has the feature that the resin is a low molecular weight comb type copolymer composed of at least the monofunctional macromonomer (MA ⁇ and the monomer (A) shown by formula (III), and has the specific acidic group at only one terminal of the main chain of the polymer.
- the monofunctional macromonomer (MA) used in the present invention is a macromonomer having a weight average molecular weight of not more than 2 ⁇ 10 4 having the polymerizable double bond group represented by formula (I) to only one terminal of the main chain of the polymer containing a least one of the polymer components represented by formula (IIa) and formula (IIb).
- hydrocarbon groups shown by a 1 , a 2 , A o , b 1 , b 2 , A 1 , B 1 , and B o each has each carbon atom number (as unsubstituted hydrocarbon group) shown in each case and these hydrocarbon groups each may have a substituent.
- a o represents --COO--, --OCO--, --CH 2 ) l1 OCO--, --CH 2 ) l2 COO-- (wherein l 1 and l 2 each represents an integer of from 1 to 3), --O--, --SO 2 --, --CO--, ##STR16## (wherein R 1 represents a hydrogen atom or a hydrocarbon group).
- Preferred examples of the hydrocarbon group represented by R 1 include an alkyl group having from 1 to 18 carbon atoms which may be substituted (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl octyl, decyl, dodecyl, hexadecyl, octadecyl, 2-chloroethyl, 2-bromoethyl, 2-cyanoethyl, 2-methoxycarbonylethyl, 2-methoxyethyl, and 3-bromopropyl), an alkenyl group having from 4 to 18 carbon atoms which may be substituted (e.g., 2-methyl-1-propenyl, 2-butenyl, 2-pentenyl, 3-methyl-2-pentenyl, 1-pentenyl, 1-hexenyl, 2-hexenyl, and 4-methyl-2-hexenyl), an aral
- the benzene ring may further be substituted.
- substituents include a halogen atom (e.g., chlorine, and bromine), an alkyl group (e.g., methyl, ethyl, propyl, butyl, chloromethyl, and methoxymethyl), and an alkoxy group (e.g., methoxy, ethoxy, propoxy, and butoxy).
- a 1 and a 2 which may be the same or different, each preferably represents a hydrogen atom, a halogen atom (e.g., chlorine, and bromine), a cyano group, an alkyl group having from 1 to 4 carbon atoms (e.g., methyl, ethyl, propyl, and butyl), --COOD 2 or --COOD 2 bonded via a hydrocarbon group, wherein D 2 represents a hydrocarbon group (preferably an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 4 to 18 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an alicyclic group having 5 to 8 carbon atoms or an aryl group having 6 to 12 carbon atoms, each of which may be substituted). More specifically, the examples of the hydrocarbon groups are those described for R 1 above.
- the hydrocarbon group through which --COOD 2 is bonded includes, for example, a methylene group, an ethylene group
- a o represents --COO--, --OCO--, --CH 2 OCO--, --CH 2 COO--, --O--, --CONH--, --SO 2 NH--, --CONHCOO--, --CONHCONH--, or ##STR18## and a 1 and a 2 , which may be the same or different, each represents a hydrogen atom, a methyl group, --COOD 3 , or --CH 2 COOD 3 , wherein D 3 represents an alkyl group having from 1 to 6 carbon atoms (e.g., methyl, ethyl, propyl, butyl, and hexyl). Most preferably, either one of a 1 and a 2 represents a hydrogen atom.
- a 1 has the same meaning as A o in formula (I) and b 1 and b 2 , which may be the same or different are the same as a 1 and a 2 in formula (I).
- B o represents an aliphatic group having from 1 to 18 carbon atoms or an aromatic group having from 6 to 12 carbon atoms.
- the aliphatic group includes an alkyl group having from 1 to 18 carbon atoms, which may be substituted, (e.g., methyl, ethyl, propyl, butyl, heptyl, hexyl, octyl, decyl, dodecyl, tridecyl, hexadecyl, octadecyl, 2-chloroethyl, 2-bromoethyl, 2-hydroxyethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-cyanoethyl, 3-chloropropyl, 2-(trimethoxysilyl)ethyl, 2-tetrahydrofuryl, 2-N,N-dimethylaminoethyl, 2-N,N-diethylaminoethyl), a cycloalkyl group having from 5 to 8 carbon atoms (e.g., cycloheptyl,
- the aromatic group shown by B o include an aryl group having from 6 to 12 carbon atoms, which may be substituted, (e.g., phenyl, tolyl, xylyl, chlorophenyl, bromophenyl, dichlorophenyl, chloromethylphenyl, methoxyphenyl, methoxycarbonylphenyl, naphthyl, and chloronaphthyl), etc.
- aryl group having from 6 to 12 carbon atoms which may be substituted, (e.g., phenyl, tolyl, xylyl, chlorophenyl, bromophenyl, dichlorophenyl, chloromethylphenyl, methoxyphenyl, methoxycarbonylphenyl, naphthyl, and chloronaphthyl), etc.
- a 1 preferably represents ##STR20##
- B o represents --CN, --CONH 2 , ##STR21## wherein J represents a hydrogen atom, a halogen atom (e.g., chlorine and bromine), an alkoxy group (e.g., methoxy, ethoxy, propoxy, and butoxy), or --COOD 4 (wherein D 4 preferably represents an alkyl group having from 1 to 8 carbon atoms, an aralkyl group having from 7 to 12 carbon atoms, or an aryl group).
- J represents a hydrogen atom, a halogen atom (e.g., chlorine and bromine), an alkoxy group (e.g., methoxy, ethoxy, propoxy, and butoxy), or --COOD 4 (wherein D 4 preferably represents an alkyl group having from 1 to 8 carbon atoms, an aralkyl group having from 7 to 12 carbon atoms, or an aryl group).
- the macromonomer (MA) may contain two or more polymer components shown by formula (IIa) and/or formula (IIb).
- a 1 in formula (IIa) is --COO--
- the content of the polymer component shown by formula (IIa) in the total polymer components of the macromonomer (MA) is at least 30% by weight.
- examples of a monomer corresponding to other repeating units copolymerizable with the polymer component represented by formula (IIa) and/or formula (IIb) are heterocyclic vinyls (e.g., vinylpyridine, vinyl imidazole, vinylpyrrolidone, vinylthiophene, vinylpyrazole, vinyl dioxane, and vinyloxazine).
- heterocyclic vinyls e.g., vinylpyridine, vinyl imidazole, vinylpyrrolidone, vinylthiophene, vinylpyrazole, vinyl dioxane, and vinyloxazine.
- the macromonomer (MA) which is used for the resin (A) of the present invention has the above-described chemical structure that the polymerizable double bond group represented by formula (I) is bonded to only one terminal of the main chain of the polymer composed of the repeating unit represented by formula (IIa) and/or formula (IIb) directly or through an appropriate linking group.
- the linking group which links the component of formula (I) and the component of formula (IIa) or (IIb) is composed of an appropriate combination of atomic group, such as a carbon-carbon bond (a single bond or a double bond), a carbon-hetero atom bond (examples of the hetero atom are oxygensulfur, nitrogen, and silicon), and a hetero atom-hetero atom bond.
- the macromonomer (MA) used in the present invention is preferably a macromonomer represented by following formula (Va) or (Vb); ##STR22## wherein a 1 , a 2 , b 1 , b 2 , A o , A 1 , B o and B 1 have the same meaning as those described above for formula (I), formula (IIa), and formula (IIb), and G represents
- R 2 and R 3 each represents a hydrogen atom, a halogen atom (e.g., fluorine, chlorine, and bromine), a cyano group, a hydroxy group, or an alkyl group (e.g., methyl, ethyl, and propyl)), ##STR24## (wherein R 4 represents a hydrogen atom or the same hydrocarbon group as that of B 1 in formula (IIa)), or a linking group composed of an optional combination of the above-described atomic group.
- R 2 and R 3 each represents a hydrogen atom, a halogen atom (e.g., fluorine, chlorine, and bromine), a cyano group, a hydroxy group, or an alkyl group (e.g., methyl, ethyl, and propyl)
- R 4 represents a hydrogen atom or the same hydrocarbon group as that of B 1 in formula (IIa)
- the weight average molecular weight of the macromonomer (MA) is higher than 2 ⁇ 10 4 , the copolymerizability with the monomer A is undesirably reduced.
- the weight average molecular weight thereof is too small, the effect of improving the electrophotographic characteristics of the photoconductive layer becomes less and, hence, the lower limit of the weight average molecular weight is preferably at least 1 ⁇ 10 3 .
- the macromonomer (MA) used in the present invention can be produced by conventionally known synthesis methods.
- a method by an ion polymerization method of forming a macromonomer by reacting various reagents with the terminal of a living polymer obtained by anionic polymerization or cationic polymerization and a method by a radical polymerization method of forming a macromonomer by reacting various reagents with an oligomer having a reactive group bonded to the terminal obtained by radical polymerization using a polymerization initiator and/or a chain transfer agent each having a reactive group such as a carboxy group, a carboxy acid chloride group, a hydroxy group, an amino group, an epoxy group, a halogen atom (e.g., bromine and iodine), etc.
- a reactive group such as a carboxy group, a carboxy acid chloride group, a hydroxy group, an amino group, an epoxy group, a halogen atom (e.g., bromine and iodine), etc.
- the macromonomer (MA) can be synthesized by the methods described in P. Dreyfuss and R. P. Quirk, Encycl. Polym. Sci. Eng., 7, 551 (1987), P. F. Rempp and E. Franta, Adu., Polym. Sci., 58, 1 (1984), V. Percec, Appl. Polym. Sci., 285, 95 (1984), R. Asami and M. Takari, Makromol. Chem. Suppl., 12, 163 (1985), P. Rempp et al., Makromol. Chem.
- a 11 represents H of CH 3
- b 11 represents H or CH 3
- b 12 represents H, --CH 3 , or --CH 2 COOH 3
- R 11 represents C i H 2i+1 (wherein i is an integer of from 1 to 18), --CH 2 C 6 H 5 , --C 6 H 5 , or ##STR25## represents --C i H 2i+1 , --CH 2 ) 3 C 6 H 5 (j is an integer of from
- R 13 represents --C i H 2i+1 , --CH 2 C 6 H 5 , or --C 6 H 5
- R 15 represents --C i H 2i+1 , --CH 2 C 6 H 5
- R 16 represents --C i H 2i+1
- E 1 represents --COOCH 3 , --C 6 H 5 , or --CN
- E 2 represents --C i H 2i+1 , --OCOC i H 2i+1 , --COOCH 3 , --C 6 H 5 ,
- E 3 represents --COOCH 3 , ##STR28## (J 2 is --CH 3 , --Cl, or --Br), or --CN, E 4 represents --Cl, --Br, --F, --OH, or --CN, E 5 represents --OCOC i H 2i+1 , --CN, --CONH 2 , or --C 6 H 5 , E 6 represents --CN, --CONH 2 , or --C 6 H 5 , E 7 represents --COOCH 3 , --C 6 H 5 , or ##STR29## J 3 represents H, --CH 3 , --Cl, --Br, --OCH 3 , or --COOCH 3 , and h represents an integer of from 2 to 4. ##STR30##
- the monomer A which is copolymerized with the above-described macromonomer (MA) is represented by formula (III).
- c 1 and c 2 which may be the same or different, have the same meaning as a 1 and a 2 in formula ⁇ I ⁇ and more preferably represent a hydrogen atom or a methyl group.
- a 2 in formula (III) has the same meaning as A 1 in (IIa) and B 2 has the same meaning as B 1 in formula (IIa).
- the composition ratio of the copolymer component composed of the macromonomer (MA) as the repeating unit to the composition unit composed of the repeating unit represented by formula (III) is preferably 1 to 90/99 to 10 (weight ratio), and more preferably 5 to 60/95 to 40.
- the binder resin (A) contains a methacrylate monomer shown by the following formula (V) (that is, the monomer represented by formula (III) wherein c 1 is a hydrogen atom, c 2 is a methyl group, and A 2 is --COO--, and hereinafter the monomer is referred to as monomer (A')) in an amount of at least from 30% by weight to 99% by weight of the total copolymer components of the resin (A); ##STR31##
- the copolymer component corresponding to the repeating unit shown by formula (III) is the methacrylate component having a specific aryl group represented by the following formula (Va) and/or formula (Vb) (the binder resin is referred to as resin (A 1 ) as described above); ##STR32##
- G 1 and G 2 each preferably represents a hydrogen atom, a chlorine atom, a bromine atom, an alkyl group having from 1 to 4 carbon atoms (e.g., methyl, ethyl, propyl, and butyl), an aralkyl group having from 7 to 9 carbon atoms (e.g., benzyl, phenethyl, 3-phenylpropyl, chlorobenzyl, dichlorobenzyl, bromobenzyl, methylbenzyl, methoxybenzyl, and chloromethylbenzyl), an aryl group (e.g., phenyl, tolyl, xylyl, bromophenyl, methoxyphenyl, chlorophenyl,
- an alkyl group having from 1 to 4 carbon atoms e.g., methyl, ethyl, propyl, and butyl
- an aralkyl group having from 7 to 9 carbon atoms e
- Z 1 is a mere chemical bond or a linking group containing from 1 to 4 linking atoms, e.g., --CH 2 ) n .sbsb.1 (n 1 represents an integer of 1, 2 or 3), --CH 2 OCO--, --CH 2 CH 2 OCO--, --CH 2 O) n .sbsb.2 (n 2 represents an integer of 1 or 2), and --CH 2 CH 2 O--, which connects --COO-- and the benzene ring.
- Z 2 has the same meaning as Z 1 in the general formula (Va).
- the content of monomer (monomer (A) other than the more preferred monomer represented by the above-described formula (V) is preferably not more than 60% by weight in the total copolymer components.
- the ratio of the copolymer components in the binder resin (A) is preferably in the following:
- Macromonomer (MA):monomer (A') of formula (V):monomer (A") of formula (III) other than monomer (A') 1 to 80:30 to 99:0 to 60 (by weight ratio).
- the binder resin (A) may further contain monomer(s) other than the above-described monomers, which can be copolymerized with macromonomer (MA) and monomer (A) as a copolymer component.
- Examples of such other monomers are ⁇ -olefins, N-substituted acrylamides, N-substituted methacrylamides (the N-substituent is hydrocarbon group and is practically the same hydrocarbon group as shown by B 1 in formula (III)), and heterocyclic vinyls (e.g., vinylpyrrolidone, vinylpyridine, vinylimidazole, vinylthiophene, vinylimidazoline, vinylpyrazole, vinyldioxane, vinylquinoline, vinylthiazole, and vinyloxazine).
- heterocyclic vinyls e.g., vinylpyrrolidone, vinylpyridine, vinylimidazole, vinylthiophene, vinylimidazoline, vinylpyrazole, vinyldioxane, vinylquinoline, vinylthiazole, and vinyloxazine.
- the content of other monomer described above does not exceed 20% by weight in the copolymer.
- the binder resin (A) used in the present invention is a polymer having at least one acidic group selected from --PO 3 H 2 , --SO 3 H, --COOH, --OH, --PO 3 RH, and cyclic acid anhydride-containing group bonded to only one terminal of the main chain of a polymer containing at least one kind of the repeating unit represented by formula (III) and at least one kind of the repeating unit shown by macromonomer (MA).
- the acidic group is bonded to one terminal of the polymer directly or through an optional linking group.
- the above-described linkage group is composed of an optional combination of atomic groups such as a carbon-carbon bond (a single bond or a double bond), a carbon-hetero atom bond (examples of the hetero atom are oxygen, sulfur, nitrogen, and silicon), and a hetero atom-hetero atom bond.
- atomic groups such as a carbon-carbon bond (a single bond or a double bond), a carbon-hetero atom bond (examples of the hetero atom are oxygen, sulfur, nitrogen, and silicon), and a hetero atom-hetero atom bond.
- the single linking group selected from the atomic groups or the linking group composed of an optional combination of the atomic groups as G in the above-described formulae (VIa) and (VIb).
- R represents a hydrocarbon group or --OR', wherein R' represents a hydrocarbon group.
- the hydrocarbon group represented by R or R' preferably includes an aliphatic group having from 1 to 22 carbon atoms (e.g., methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl, octadecyl, 2-chloroethyl, 2-methoxyethyl, 3-ethoxypropyl, allyl, crotonyl, butenyl, cyclohexyl, benzyl, phenethyl, 3-phenylpropyl, methylbenzyl, chlorobenzyl, fluorobenzyl, and methoxybenzyl) and a substituted or unsubstituted aryl group (e.g., phenyl, tolyl, ethylpheny
- aryl group e.
- the cyclic acid anhydride-containing group is a group containing at least one cyclic acid anhydride.
- the cyclic acid anhydride to be contained includes an aliphatic dicarboxylic acid anhydride and an aromatic dicarboxylic acid anhydride.
- aliphatic dicarboxylic acid anhydrides include succinic anhydride ring, glutaconic anhydride ring, maleic anhydride ring, cyclopentane-1,2-dicarboxylic acid anhydride ring, cyclohexane-1,2-dicarboxylic acid anhydride ring, cyclohexene-1,2-dicarboxylic acid anhydride ring, and 2,3-bicyclo[2,2,2]octanedicarboxylic acid anhydride.
- These rings may be substituted with, for example, a halogen atom (e.g., chlorine and bromine) and an alkyl group (e.g., methyl, ethyl, butyl, and hexyl).
- aromatic dicarboxylic acid anhydrides include phthalic anhydride ring, naphtnalene-dicarboxylic acid anhydride ring, pyridinedicarboxylic acid anhydride ring and thiophenedicarboxylic acid anhydride ring.
- These rings may be substituted with, for example, a halogen atom (e.g., chlorine and bromine), an alkyl group (e.g., methyl, ethyl, propyl, and butyl), a hydroxyl group, a cyano group, a nitro group, and an alkoxycarbonyl group (e.g., methoxycarbonyl and ethoxycarbonyl).
- a halogen atom e.g., chlorine and bromine
- an alkyl group e.g., methyl, ethyl, propyl, and butyl
- a hydroxyl group e.g., methyl, ethyl, propy
- binder resin (A) as a method of bonding the acidic group to one terminal of the polymer main chain, there are a method of reacting various reagents to the terminal of a living polymer obtained by a conventionally known anionic polymerization or a cationic polymerization (method by ionic polymerization), a method of performing a radical polymerization using a polymerization initiator and/or a chain transfer agent each having the specific acidic group in the molecule (method by radical polymerization), and a method of forming a polymer having a reactive group (e.g., an amino group, a halogen atom, an epoxy group, and an acid halide group) at the terminal thereof by an ionic polymerization or a radical polymerization and converting the reactive group to the specific acidic group in the present invention by a high molecular reaction.
- a reactive group e.g., an amino group, a halogen atom, an epoxy group, and an acid halide group
- the chain transfer agent are a mercapto compound having the acidic group or the above-described reactive group, which can be induced into the acidic group later, (e.g., thioglycolic acid, thiomalic acid, thiosalicyclic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N-(2-mercaptopropionic)glycine, 2-mercaptonicotinic acid, 3-[N-(2-mercaptoethyl)carbamoyl]propionic acid, 3-[N-(2-mercaptoethyl)amino]propionic acid, N-(3-mercaptopropionyl)alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, 2-mercaptoethanol, 2-mercapto-1,2-propanediol, 1-mercapto-2-propane
- polymerization initiator having the acidic group or the specific reactive group are 4,4'-azobis(4-cyanovaleric acid), 4,4'-azabis(4-cyanovaleric acid chloride), 2,2'-azobis-(2-cyanopropanol), 2,2'-azobis(2-cyanopentanol), 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)-propioamido], 2,2'-azobis ⁇ 2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]-propioamido ⁇ , 2,2'-azobis-2-[1-(2-hydroxyethyl)-2-imidazolin-2-yl]propane, 2,2'azobis[2-(2-imidazolin-2-yl)-propane], and 2,2'-azobis[2-(4,5,6,7-tetrahydro-1H-1,3-diazopin-2-yl)propane].
- the amount of the chain transfer agent or the polymerization initiator is from 0.5 to 10 parts by weight, and preferably from 1 to 5 parts by weight to 100 parts by weight of the total monomers.
- binder resin (B) used in the present invention is described in detail.
- monofunctional macromonomer (M) which is used for the binder resin (B) is more practically explained.
- acidic groups are --COOH, --SO 3 H, phenolic OH, and ##STR36##
- the acidic group is ##STR37##
- the acidic group has the same meaning as those described above in the binder resin (A).
- phenolic hydroxy group described above examples include a hydroxy group of hydroxy-substituted aromatic compounds containing a polymerizable double bond and a hydroxy group of (meth)acrylic acid esters and amides each having a hydroxyphenyl group as a substituent.
- the cyclic acid anhydride-containing group is a group having at least one cyclic acid anhydride and as the cyclic acid anhydride, there are aliphatic dicarboxylic acid anhydride and aromatic dicarboxylic acid anhydride.
- Examples of the aliphatic dicarboxylic acid anhydride are a succinic anhydride ring, a glutaconic anhydride ring, a maleic anhydride ring, a cyclopentane-1,2-dicarboxylic acid anhydride ring, a cyclohexane-1,2-dicarboxylic acid anhydride ring, and a cyclohexene-1,2-dicarboxylic acid anhydric ring, and a 2,3-bicyclo-[2,2,2]octandicarboxylic acid anhydride ring.
- These rings may be substituted with a halogen atom (e.g., chlorine and bromine) or an alkyl group (e.g., methyl, ethyl, butyl, and hexyl).
- examples of the aromatic dicarboxylic acid anhydride are a phthalic anhydride ring, a naphthalenedicarboxylic acid anhydride ring, a pyridinedicarboxylic acid anhydride ring, and a thiophene-dicarboxylic acid anhydride ring.
- These rings may be substituted with a halogen atom (e.g., chlorine and bromine), an alkyl group (e.g., methyl, ethyl, propyl, and butyl), a hydroxy group, a cyano group, a nitro group, an alkoxycarbonyl group (examples of the alkoxy group are methoxy and ethoxy), etc.
- a halogen atom e.g., chlorine and bromine
- an alkyl group e.g., methyl, ethyl, propyl, and butyl
- a hydroxy group e.g., methyl,
- Two or more kinds of the above-described polymer components each containing the specific acidic group can be included in the A block.
- two or more kinds of these acidic group-containing polymer components may be present in the form of a random copolymer or a block copolymer.
- components having no acidic group may be contained in the A block, and examples of such components include the components represented by the general formula (IV) described in detail below.
- the content of the component having no acidic group in the A block is preferably from 0 to 50% by weight, and more preferably from 0 to 20% by weight. It is most preferred that such a component is not contained in the A block.
- the components constituting the B block in the present invention include at least a repeating unit represented by the general formula (IV) described above.
- X 3 represents --COO--, --OCO--, --CH 2 ) l .sbsb.3 OCO--, --CH 2 ) l .sbsb.4 COO-- (wherein l 3 and l 4 each represents an integer of from 1 to 3), ##STR38## (wherein R 23 represents a hydrogen atom or a hydrocarbon group).
- Preferred examples of the hydrocarbon group represented by R 23 include an alkyl group having from 1 to 18 carbon atoms which may be substituted (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl octyl, decyl, dodecyl, hexadecyl, octadecyl, 2-chloroethyl, 2-bromoethyl, 2-cyanoethyl, 2-methoxycarbonylethyl, 2-methoxyethyl, and 3-bromopropyl), an alkenyl group having from 4 to 18 carbon atoms which may be substituted (e.g., 2-methyl-1-propenyl, 2-butenyl, 2-pentenyl, 3-methyl-2-pentenyl, 1-pentenyl, 1-hexenyl, 2-hexenyl, and 4-methyl-2-hexenyl), an aral
- R 21 represents a hydrocarbon group, and preferred examples thereof include those described for R 23 .
- X 3 represents ##STR39## in the general formula (IV), R 21 represents a hydrogen atom or a hydrocarbon group.
- the benzene ring may further be substituted.
- substituents include a halogen atom (e.g., chlorine, and bromine), an alkyl group (e.g., methyl, ethyl, propyl, butyl, chloromethyl, and methoxymethyl), and an alkoxy group (e.g., methoxy, ethoxy, propoxy, and butoxy).
- d 1 and d 2 which may be the same or different, each preferably represents a hydrogen atom, a halogen atom (e.g., chlorine, and bromine), a cyano group, an alkyl group having from 1 to 4 carbon atoms (e.g., methyl, ethyl, propyl, and butyl), --COOR 24 or --COOR 24 bonded via a hydrocarbon group, wherein R 24 represents a hydrocarbon group (preferably an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 4 to 18 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an alicyclic group having 5 to 8 carbon atoms or an aryl group having 6 to 12 carbon atoms, each of which may be substituted). More specifically, the examples of the hydrocarbon groups are those described for R 23 above.
- the hydrocarbon group via which --COOR 24 is bonded includes, for example, a methylene group, an alkyl group having from 1
- X 3 represents --COO--, --OCO--, --CH 2 OCO--, --CH 2 COO--, --O--, --CONH--, --SO 2 NH-- or ##STR41## and d 1 and d 2 , which may be the same or different, each represents a hydrogen atom, a methyl group, --COOR 24 , or --CH 2 COOR 24 , wherein R 24 represents an alkyl group having from 1 to 6 carbon atoms (e.g., methyl, ethyl, propyl, butyl, and hexyl). Most preferably, either one of d 1 and d 2 represents a hydrogen atom.
- the B block which is constituted separately from the block A which is composed of the polymer component containing the above-described specific acidic group may contain two or more kinds of the repeating units represented by the general formula (IV) described above and may further contain polymer components other than these repeating units.
- the polymerizable components may be contained in the B block in the form of a random copolymer or a block copolymer, but are preferably contained at random therein.
- any components copolymerizable with polymer component of the repeating units can be used.
- Suitable examples of monomer corresponding to the repeating unit copolymerizable with the polymer component represented by the general formula (IV), as a polymerizable component in the B block include acrylonitrile, methacrylonitrile and heterocyclic vinyl compounds (e.g., vinylpyridine, vinylimidazole, vinylpyrrolidone, vinylthiophene, vinylpyrazole, vinyldioxane, and vinyloxazine).
- Such other monomers are employed in a range of not more than 20 parts by weight per 100 parts by weight of the total polymerizable components in the B block.
- the B block does not contain the polymerizable component containing the acidic group which is a component constituting the A block.
- the macromonomer (M) to be used in the present invention has a structure of the AB block copolymer in which a polymerizable double bond group is bonded to one of the terminals of the B block composed of the polymerizable component represented by the general formula (IV) and the other terminal thereof is connected to the A block composed of the polymerizable component containing the acidic group.
- the polymerizable double bond group will be described in detail below.
- Suitable examples of the polymerizable double bond group include those represented by the following general formula (VIII): ##STR42## wherein X 5 has the same meaning as X 3 defined in the general formula (IV)/ and d 5 and d 6 , which may be the same or different, each has the same meaning as d 1 and d 2 defined in the general formula (IV).
- the macromonomer (M) used in the present invention has a structure in which a polymerizable double bond group preferably represented by the general formula (VIII) is bonded to one of the terminals of the B block either directly or through an appropriate linking group.
- the linking group which can be used includes a carbon-carbon bond (either single bond or double bond), a carbon-hetero atom bond (the hetero atom includes, for example, an oxygen atom, a sulfur atom, a nitrogen atom, and a silicon atom), a hetero atom-hetero atom bond, and an appropriate combination thereof.
- R 25 and R 26 each represents a hydrogen atom, a halogen atom (e.g., fluorine, chlorine, and bromine), a cyano group, a hydroxyl group, or an alkyl group (e.g.,
- R 27 and R 28 each represents a hydrogen atom or a hydrocarbon group having the same meaning as defined for R 21 in the general formula (IV) described above), and an appropriate combination thereof.
- the macromonomer (M) preferably has a weight average molecular weight of at least 1 ⁇ 10 3 .
- the macromonomer (M) used in the present invention can be produced by a conventionally known synthesis method. More specifically, it can be produced by the method comprising previously protecting the acidic group of a monomer corresponding to the polymer component having the specific acidic group to form a functional group, synthesizing an AB block copolymer by a so-called known living polymerization reaction, for example, an ion polymerization reaction with an organic metal compound (e.g., alkyl lithiums, lithium diisopropylamide, and alkylmagnesium halides) or a hydrogen iodide/iodine system, a photopolymerization reaction using a porphyrin metal complex as a catalyst, or a group transfer polymerization reaction, introducing a polymerizable double bond group into the terminal of the resulting living polymer by a reaction with a various kind of reagent, and then conducting a protection-removing reaction of the functional group which has been formed by protecting the acidic group by a hydrolysis reaction
- the living polymer can be easily synthesized according to synthesis methods as described, e.g., in P. Lutz, P. Masson et al, Polym. Bull., 12, 79 (1984), B. C. Anderson, G. D. Andrews et al, Macromolecules, 14, 1601 (1981), K. Hatada, K. Ute et al, Polym.
- the protection of the specific acidic group of the present invention and the release of the protective group can be easily conducted by utilizing conventionally known techniques. More specifically, they can be performed by appropriately selecting methods as described, e.g., in Yoshio Iwakura and Keisuke Kurita, Hannosei Kobunshi (Reactive Polymer), published by Kodansha (1977), T. W. Greene, Protective Groups in Organic Synthesis, published by John Wiley & Sons (1981), and J. F. W. McOmie, Protective Groups in Organic Chemistry, Plenum Press, (1973), as well as methods as described in the above references.
- the AB block copolymer can be also synthesized by a photoinfeter polymerization method using a dithiocarbamate compound as an initiator.
- the block copolymer can be synthesized according to synthesis methods as described, e.g., in Takayuki Otsu, Kobunshi (Polymer), 37, 248 (1988), Shunichi Himori and Ryuichi Ohtsu, Polym. Rep. Jap. 37, 3508 (1988), JP-A-64-111, and JP-A-64-26619.
- the macromonomer (M) according to the present invention can be obtained by applying the above described synthesis method for macromonomer to the AB block copolymer.
- the monomer copolymerizable with the macromonomer (M) described above is preferably selected from those represented by the general formula (VI) described above.
- d 3 , d 4 , X 4 and R 22 each has the same meaning as defined for d 1 , d 2 , X 3 and R 21 in the general formula (IV) as described above. More preferably, d 3 represents a hydrogen atom, d 4 represents a methyl group, and X 2 represents --COO--.
- a ratio of the A block to the B block in the macromonomer (M) preferably ranges from 1 to 30/99 to 70 by weight.
- the content of the acidic group-containing component in the resin (B) is preferably from 0.1 to 20% by weight, more preferably from 0.5 to 10% by weight.
- a ratio of the copolymerizable component having the macromonomer (M) as a repeating unit to the copolymerizable component having the monomer represented by the general formula (VI) as a repeating unit ranges preferably from 1 to 60/99 to 40 by weight, more preferably 5 to 50/95 to 50 by weight.
- the binder resin for the photoconductive layer of the electrophotographic material of the present invention is composed of at least the binder resin (A) and the binder resin (B).
- the binder resin is composed of at least the binder resin (A') and the binder resin (B) is described in detail.
- the binder resin (B) is the same as that for the embodiment of the present invention described above, the detailed description of the binder resin (B) is omitted.
- the binder resin in the embodiment of the present invention is composed of at least the binder resin (A'), that is, low molecular weight graft copolymer (A') having at least monofunctional macromonomer (MA') and a monomer represented by the above-described formula (III) and the high molecular weight binder resin (B).
- the graft type copolymer used as the binder resin (A') may have at least one acidic group selected
- binder resin (A 1 ') From --PO 3 H 2 , --SO 3 H, --COOH, --OH, and ##STR53## (wherein R 3 ' has the same meaning as R described above) (hereinafter, the resin (A') is referred to as binder resin (A 1 ')).
- the high molecular weight binder resin (B) is a graft type copolymer containing at least one of the above-described macromonomers (M) and the polymer component represented by the formula (VI) described above.
- the conventional acidic group-containing binder resins described above are mainly for offset master plates, the molecular weight of the resin is high (e.g., higher than 5 ⁇ 10 4 ) for improving the printing resistance by keeping a high film strength, and the copolymer of the binder resin is a random copolymer wherein acidic group-containing copolymer components randomly exist in the main chain of the polymer.
- the binder resin (A') which is used for the binder resin in the present invention is a graft type copolymer and the acidic groups contained in the resin do not randomly exist in the polymer main chain but are contained in the graft portion of the polymer.
- the portions of the acidic groups existing at the specific position apart from the main chain of the polymer adsorb to the stoichiometric defects of an inorganic photoconductive substance and the main chain portion of the polymer mildly and sufficiently cover or coat the surface of the photoconductive substance. It has been found that by the above phenomenon, the traps of the photoconductor are compensated and improve the humidity characteristics as well as the photoconductive particles can be sufficiently dispersed to prevent the occurrence of the aggregation of the particles, and also even when the environmental condition is greatly changed from high temperature and high humidity to low temperature and low humidity, stable electrophotographic characteristics of a high performance are maintained.
- the binder resin (B) improves sufficiently the mechanical strength of the photoconductive layer, the mechanical strength thereof being insufficient by the resin (A') only, without hindering the high performance of the electrophotographic characteristics by the use of the binder resin (A').
- the binder resin used in the present invention is particularly effective in the case of a scanning exposure system using a semiconductor laser.
- the binder resin for the photoconductive layer in the present invention by specifying the weight average molecular weight and the structure of the graft portion of each of the binder resin (A') and the binder resin (B) as the binder resin for the photoconductive layer in the present invention, and also the content of the acidic groups specifically contained in the resin, the strength of the interaction between the inorganic photoconductive substance and the resins and the facilitation of the interaction of the polymer molecular chains of the binder resin (A') and the binder resin (B) can be changed.
- the molecular chains of the macromonomer (MA') component (graft portion) of the binder resin (A') and the monomer component (main chain portion) of formula (III) cause a sufficient interaction with the molecular chain of the component of the main chain portion of the binder resin (B), and further the molecular chains of the macromonomer (M)
- the electrophotographic characteristics are greatly improved mainly by the action of the binder resin (A') and the mechanical strength of the photoconductive layer is improved by the action of the binder resin (B). Also, it is assumed that, in the binder resin (B), the acidic group bonded to the specific position of the polymer main chain causes a mild interaction with the inorganic photoconductive substance to an extent of not hindering the electrophotographic characteristics thereof.
- the surface of the photoconductive layer is smoothed.
- an electrophotographic photosensitive material having a photoconductive layer of rough surface is used as a lithographic printing master plate by an electrophotographic system
- the dispersion state of the particles of a photoconductive substance such as zinc oxide and a binder resin is not adequate, whereby, when the photosensitive layer is subjected to an oil-desensitizing treatment with an oil-desensitizing solution, the non-image areas are not uniformly rendered hydrophilic to cause attaching of a printing ink to the non-image areas at printing, which results in the occurrence of background stains in the non-image areas.
- the interaction of the adsorption and coating of the inorganic photoconductive substance and the binder resin is adequately performed and also the high film strength of the photoconductive layer is maintained.
- the binder resin (A') used in the present invention has higher light sensitivity than a random copolymer resin having acidic groups at the side chains bonded to the polymer main chain.
- spectral sensitizing dyes which are used for having a light sensitivity at the region of from visible light to infrared light sufficiently function the spectral sensitizing actions by adsorbing onto a photoconductive substance
- the binder resin containing the copolymer of the present invention causes an adequate interaction with an inorganic photoconductive substance without hindering the adsorption of spectral sensitizing dyes to the photoconductor.
- This action is particularly remarkable for cyanine dyes or phthalocyanine series pigments which are particularly effective as spectral sensitizing dyes for the regions of near infrared to infrared.
- the binder resin When the low molecular weight resin (A') is used alone as a binder resin, the binder resin sufficiently adsorbs onto an inorganic photoconductive substance and covers the surfaces of the photoconductive particles, whereby the photoconductive layer shows good surface smoothness and electrostatic characteristics, images having no background staining are obtained. Further, a sufficient film strength as a CPC photosensitive material or as an offset printing master plate for printing several thousands prints is maintained.
- the resin (B) together with the resin (A') according to the present invention the mechanical strength of the photoconductive layer, the mechanical strength thereof being yet insufficient by the resin (A') alone, can be more improved without adversely affecting the functions of the resin (A').
- the electrophotographic photosensitive material of the present invention show excellent electrostatic characteristics even when the environmental condition is deviated, has a sufficiently high film strength, and can print at least 7000 prints having good image quality even under severe printing condition (e.g., when the printing pressure is increased by using a large printing machine).
- the film strength is more improved whereby an improved printing resistance can be obtained.
- the weight average molecular weight of the graft type copolymer is from 1 ⁇ 10 3 to 2 ⁇ 10 4 , and preferably from 3 ⁇ 10 3 to 1 ⁇ 10 4
- the content of the copolymer component of the macromonomer (M) is from 1 to 80% by weight, and preferably from 5 to 70% by weight.
- the acidic group is bonded to the terminal of the main chain of the copolymer
- the content of the acidic group in the copolymer is from 0.5 to 15% by weight, and preferably from 1 to 10% by weight.
- the glass transition point of the binder resin (A') is preferably from -20° C. to 120° C., and more preferably from +10° C. to 90° C.
- the molecular weight of the binder resin (A') is less than 1 ⁇ 10 3 , the film-forming ability of the resin is reduced, whereby a sufficient film strength cannot be maintained, while, if the molecular weight is larger than 2 ⁇ 10 4 , the electrophotographic characteristics (in particular, the initial potential and the dark decay retention) are undesirably deteriorated.
- the electrophotographic characteristics in particular, the initial potential and the dark decay retention
- the electrophotographic characteristics are greatly deteriorated and, when the photosensitive material is used as an offset master plate, the occurrence of background stains becomes severe.
- the content of optional acidic groups (optional acidic groups at the terminal of the main chain) in the binder resin (A') is less than 0.5% by weight, the initial potential is low and sufficient image density cannot be obtained.
- the content of the acidic group is higher than 15% by weight, the dispersibility is lowered, the smoothness of the surface of the photoconductive layer and the high humidity characteristics of the electrophotographic characteristics are lowered, and, further, when the photosensitive material is used as an offset printing master plate, the occurrence of background stains increases.
- the monofunctional macromonomer (MA') which is used as the copolymer component of the binder resin (A') i.e., the graft type copolymer used in the present invention is explained practically.
- the monofunctional macromonomer (MA') is a macromonomer having a weight average molecular weight of not more than 2 ⁇ 10 4 having the polymerizable double bond group represented by the formula (I) bonded to only one terminal of the main chain of the polymer containing at least one kind of the polymer components represented by the formulae (IIa) and (IIb) and at least one of polymer components each having the specific acidic group such as ##STR54##
- any vinylic compound having the above-described polar group can be used.
- these compounds are, for example, described in Polymer Data Handbook (Foundation), edited by Kobunshi Gakkai, published by Baifukan K.K., 1986.
- vinyl compounds are acrylic acid, ⁇ and/or ⁇ -substituted acrylic acid (e.g., ⁇ -acetoxyacrylic acid, ⁇ -acetoxymethylacrylic acid, ⁇ -(2-amino)ethylacrylic acid, ⁇ -chloroacrylic acid, ⁇ -bromoacrylic acid, ⁇ -fluoroacrylic acid, ⁇ -tributylsilylacrylic acid, ⁇ -cyanoacrylic acid, ⁇ -chloroacrylic acid, ⁇ -bromoacrylic acid, ⁇ -fluoroacrylic acid, ⁇ -methoxyacrylic acid, and ⁇ , ⁇ -dichloroacrylic acid), methacrylic acid, itaconic acid, itaconic acid half esters, itaconic acid half amides, crotonic acid, 2-alkenylcarboxylic acids (e.g., 2-pentenoic acid, 2-methyl-2-hexenoic acid, 2-octenoic acid,
- the --OH group includes the phenolic hydroxy group such as a hydroxy group of hydroxy-substituted aromatic compounds containing a polymerizable double bond and a hydroxy group of (meth)acrylic acid esters and amides each having a hydroxyphenyl group as a substituent, and a hydroxy group of alcohols containing a vinyl group or allyl group (e.g., allyl alcohol), a hydroxy group of (meth)acrylates containing --OH group in an ester substituent thereof, and a hydroxy group of (meth)acrylamides containing --OH group in an N-substituent thereof).
- a represents --H, --CH 3 , --Cl, --Br, --CN, --CH 2 COOCH 3 , or --CH 2 COOH;
- b represents --H or --CH 3 ;
- j represents an integer of from 2 to 18;
- k represents an integer of 2 to 5;
- h represents an integer of from 1 to 4; and
- i represents an integer of 1 to 12.
- the content of the copolymer components having the above-described polar group contained in the macromonomer (MA') is preferably from 0.5 to 50 parts by weight, and more preferably from 1 to 40 parts by weight per 100 parts by weight of the total copolymer components in the macromonomer (MA').
- the total content of the acidic group-containing component contained in the total grafted portions in the resin (A') is preferably from 0.1 to 10 parts by weight per 100 parts by weight of the total copolymer components in the resin (A').
- the resin (A') has the acidic group selected from --COOH, --SO 3 H, and --PO 3 H 2
- the total content of the components having the acidic group in the grafted portions of the resin (A') is more preferably from 0.1 to 5 parts by weight.
- the macromonomer (MA') may further contain other copolymer component(s) in addition to the above-described copolymer components.
- acrylonitrile methacrylonitrile
- acrylamides methacrylamides
- styrene styrene derivatives
- heterocyclic vinyls e.g., vinylpyridine, vinylimidazole, vinylpyrrolidone, vinylthiophene, vinylpyrazole, vinyldioxane and vinyloxazine.
- the content of such monomers is preferably from 1 to 20 parts by weight per 100 parts by weight of the total copolymer components in the macromonomer (MA').
- the macromonomer (MA') used in the present invention has a chemical structure that the polymerizable double bond group represented by formula (I) is bonded directly or by an optional linking group to only one terminal of the main chain of the random polymer composed of at least the repeating unit shown by formula (IIa) and/or the repeating unit shown by formula (IIb) and at least the repeating unit having the specific acidic group.
- the linking group which connects the component represented by formula (I) and the component shown by (IIa) or (IIb) or the acidic group-containing component includes a carbon-carbon bond (single bond or double bond), carbon-hetero atom bond (examples of the hetero atom are oxygen, sulfur, nitrogen, and silicon), and a hetero atom-hetero atom bond, or an optional combination of these atomic groups.
- linking group is a
- R 12 and R 13 each represents a hydrogen atom, a halogen atom (e.g., fluorine, chlorine, and bromine), a cyano group, a hydroxy group, or an alkyl group (e.g., methyl, ethyl,
- R 14 which may be the same or different, each represents a hydrogen atom or the same hydrocarbon group as described above for B 1 in formula (IIa)) and a linking group composed of an optional combination of 2 or more these atomic groups.
- the weight average molecular weight of the macromonomer (MA') exceeds 2 ⁇ 10 4 , the copolymerizing property with the monomer shown by formula is undesirably reduced.
- the weight average molecular weight of the macromonomer (MA') is too low, the effect of improving the electrophotographic characteristics of the photoconductive layer is reduced.
- the weight average molecular weight is preferably from 1 ⁇ 10 3 to 2 ⁇ 10 4 .
- the macromonomer (MA') used in the present invention can be produced by conventional synthesis methods.
- the macromonomer (MA') can be synthesized by a radical polymerization method of forming the macromonomer by reacting an oligomer having a reactive group bonded to the terminal and various reagent.
- the oligomer used above can be obtained by a radical polymerization using a polymerization initiator and/or a chain transfer agent each having a reactive group such as a carboxy group, a carboxyhalide group, a hydroxy group, an amino group, a halogen atom, an epoxy group, etc., in the molecule thereof.
- the macromonomer (MA') used in the present invention has the above-described polar group as the compounds of the repeating unit, the following matters should be considered in the synthesis thereof.
- the radical polymerization and the introduction of a terminal reactive group are carried out by the above-described method using a monomer having the acidic group as the form of a protected functional group as shown, for example, in the following reaction formula (I). ##STR60##
- the reaction for introducing the protective group and the reaction for removal of the protective group e.g., hydrolysis reaction, hydrogenolysis reaction, and oxidation-decomposition reaction
- polar group ##STR61## being randomly contained in the macromonomer (MA') used in the invention can be carried out by any of conventional known methods.
- JP-A-62-212669 JP-A-62-286064, JP-A-62-210475, JP-A-62-195684, JP-A-62-258476, JP-A-63-260439, JP-A-1-63977, and JP-A-1-70767.
- Another method for producing the macromonomer (MA') comprises synthesizing the oligomer by the same manner as described above and then reacting the oligomer with a reagent having a polymerizable double bond group which reacts with only "specific reactive group” bonded to one terminal by utilizing the difference between the reactivity and the "specific reactive group” and the reactivity of the polar group contained in the oligomer as shown in the following reaction formula (II). ##STR62##
- Moiety A is a functional group in the reagent for introducing a polymerizable group
- Moiety B is a specific functional group at the terminal of oligomer
- Moiety C is a acidic group in the repeating unit in the oligomer.
- the chain transfer agent which can be used for producing the above-described macromonomer (MA') includes, for example, mercapto compounds having a substituent capable of being induced into the polar group later (e.g., thioglycolic acid, thiomalic acid, thisalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N-(2-mercaptopropionyl)glycine, 2-mercaptonicotinic acid, 3-[N-(2-mercaptoethyl)carbamoylpropionic acid, 3-[N-(2-mercaptoethyl)amino]propionic acid, N-(3-mercaptopropionyl)alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-
- the polymerization initiator having a specific reactive group which can be used for the production of the above-described macromonomer, include, for example, 2,2'-azobis(2-cyanopropanol), 2,2'-azobis(2-cyanopentanol), 4,4'-azobis(4-cyanovaleric acid), 4,4'-azobis(4-cyanovaleric acid chloride), 2,2'-azobis[2-(5-methyl-2-imidazolin-2-yl)propane], 2,2'-azobis[2-(2-imidazolin-2-yl)propanol], 2,2'-azobis[2-(2-imidazolin-2-yl)propanol], 2,2'-azobis[2-(2-imidazolin-2-yl)propanol], 2,2'-azobis[2-(3,4,5,6,-tetrahydropyrimidin-2-yl)propane], 2,2'-azobis[2-[1,2-hydroxyethyl)-2-imidazol
- the chain transfer agent or the polymerization initiator is used in an amount of from 0.1 to 15 parts by weight, and preferably from 0.5 to 10 parts by weight per 100 parts by weight of the total monomers.
- macromonomer (MA') used in the present invention are illustrated below, but the present invention is not limited thereto.
- b represents --H or --CH 3
- d represents --H, --CH 3 , or --CH 2 COOCH 3
- R represents --C n H 2n+1 (wherein n represents an integer of from 1 to
- Y 1 and Y 2 each represents ##STR70##
- W 2 represents --Cl, --Br, --CN, or --OCH 3 ;
- e represents an integer of from 2 to 18;
- f represents an integer of from 2 to 12; and
- g represents an integer of 2 to 4.
- c 1 and c 2 which may be the same or different, have the same significance as a 1 and a 2 in formula (I) and A 2 and B 2 have the same meaning as A 1 and B 1 in formula (IIa), respectively.
- the composition ratio of the copolymer component composed of the macromonomer (MA') as the repeating unit and the copolymer component composed of the monomer shown by formula (III) as the repeating unit is preferably from 5 to 70/95 to 30 by weight ratio, and more preferably from 10 to 60/90 to 40 by weight ratio.
- the binder resin (A') used in the present invention may further contain monomers other than the macromonomer (MA') and the monomer of formula (III) as a further copolymer component together with the macromonomer and the monomer.
- Examples of such other monomer are ⁇ -olefins, alkanoic acid vinyl esters, alkanoic acid allyl esters, acrylonitrile, methacrylonitrile, vinyl ethers, acrylamides, methacrylamides, styrenes, and heterocyclic vinyls (e.g., vinylpyrrolidone, vinylpyridine, vinylimidazole, vinylthiophene, vinylimidazoline, vinylpyrazole, vinyldioxane, vinylquinoline, vinylthiazole, and vinyloxazine).
- vinylpyrrolidone vinylpyridine
- vinylimidazole vinylthiophene
- vinylimidazoline vinylpyrazole
- vinyldioxane vinylquinoline
- vinylthiazole and vinyloxazine
- the content of monomers other than the macromonomer (MA') and the monomer of formula (III) is not more than 20% by weight of the copolymer.
- the content of the copolymer component corresponding to the macromonomer (MA') is less than 1% by weight, the dispersion of the coating composition for the photoconductive layer becomes insufficient. Also, the content exceeds 80% by weight, the copolymerization with the monomer of formula (III) does not sufficiently proceeds, whereby polymers of the monomer of formula (III) only or other monomers only undesirably form in addition to the desired graft copolymer. Furthermore, if the photoconductive particles are dispersed using such a resin as the binder resin, aggregates of the resin and the photoconductive particles tend to form.
- the binder resin (A') may be a copolymer (binder resin (A 1 ') having at least one of the polar group selected from --PO 3 H 2 , --SO 3 H, --COOH, --OH, and ##STR72## at only one terminal of the main chain of the polymer containing at least one of the repeating unit represented by formula (III) and at least one of the macromonomer (MA') as a repeating unit.
- binder resin (A') may be a copolymer (binder resin (A 1 ') having at least one of the polar group selected from --PO 3 H 2 , --SO 3 H, --COOH, --OH, and ##STR72## at only one terminal of the main chain of the polymer containing at least one of the repeating unit represented by formula (III) and at least one of the macromonomer (MA') as a repeating unit.
- the binder resin (A') may be used together with the binder resin (A 1 ').
- --OH and ##STR73## have the same meaning as --OH and ##STR74## described above for the acidic group-containing polymer component of the resin (A').
- the acidic group is bonded to one terminal of the polymer main chain directly or through an appropriate linking group.
- the linking group is composed of an appropriate combination of atomic groups such as a carbon-carbon bond (a single bond or a double bond), a carbon-hetero atom bond (examples of the hetero atom are oxygen, sulfur, nitrogen, and silicon).
- atomic groups such as a carbon-carbon bond (a single bond or a double bond), a carbon-hetero atom bond (examples of the hetero atom are oxygen, sulfur, nitrogen, and silicon).
- R 18 to R 20 have the same meaning as R 12 to R 14 described above) or is composed of a combination of two or more the atomic groups.
- the binder resin (A 1 ') having the acidic group at the terminal of the polymer main chain can be synthesized by using a polymerization initiator or a chain transfer agent each having the acidic group or a specific reactive group which can be induced to the acidic group later at the polymerization reaction of at least the above-described macromonomer (MA') and the monomer represented by formula (III).
- the resin (A 1 ') can be obtained in the same manner as the above-described method for obtaining the oligomer having the reactive group at the terminal.
- the binder resin used in the present invention may contain two or more kinds of the above-described binder resin (A') (including the binder resin (A')).
- the weight average molecular weight of the binder resin (B) is from 3 ⁇ 10 4 to 1 ⁇ 10 6 , and preferably from 5 ⁇ 10 4 to 5 ⁇ 10 5 .
- the content of the monofunctional macromonomer composed of the AB type block copolymer component in the copolymer of the resin (B) is from 1 to 60% by weight, and more preferably from 5 to 50% by weight. Furthermore, the content of the polymer component represented by formula (V) is preferably from 40 to 99% by weight, and more preferably from 50 to 95% by weight.
- the glass transition point of the binder resin (B) is preferably from 0° C. to 110° C., and more preferably from 20° C. to 90° C.
- the molecular weight of the binder resin (B) is less than 3 ⁇ 10 4 , a sufficient film strength cannot be maintained, while, if the molecular weight is larger than 1 ⁇ 10 6 , the dispersibility is reduced and the smoothness of the surface of the photoconductive layer is reduced, whereby the image quality of duplicated images is deteriorated (in particular, the reproducibility of fine lines and letters is lowered) and, further, when the light-sensitive material is used as an offset printing master plate, the occurrence of background stains becomes severe.
- the content of the macromonomer in the binder resin (B) is less than 1% by weight, the electrophotographic characteristics (in particular, dark decay ratio and light sensitivity) are reduced and also the deviation of the electrophotographic characteristics under environmental condition becomes larger in the combination with spectral sensitizing dyes for the region of from near infrared to infrared.
- the reason therefor is considered that the content of the macromonomer which forms the graft portion becomes low, thereby resulting in the formation of almost the same composition as a conventional homopolymer or random copolymer.
- the content of the macromonomer exceeds 60% by weight, the copolymerability of monomers corresponding to the other copolymer components and the macromonomer of the present invention is insufficient and, when the resin is used as a binder resin for photoconductive layer, sufficient electrophotographic characteristics cannot be obtained.
- the binder resins (A) or (A') and (B) according to the present invention can be produced by copolymerization of the corresponding mono-functional polymerizable compounds at the desired ratio.
- the copolymerization can be performed using a known polymerization method, for example, solution polymerization, suspension polymerization, precipitation polymerization, and emulsion polymerization. More specifically, according to the solution polymerization, monomers are added to a solvent such as benzene or toluene at the desired ratio and polymerized with an azobis compound, a peroxide compound or a radical polymerization initiator to prepare a copolymer solution. The solution is dried or added to a poor solvent whereby the desired copolymer can be obtained.
- the synthesis of the low molecular weight binder resin (A) or (A') and the high molecular weight binder resin (B) can be easily controlled by the kind of the initiator, the amount of the initiator, the polymerization initiation temperature, and/or the use of a chain transfer agent.
- a resin which is conventionally used as a binder resin for electrophotographic light-sensitive materials can be employed in combination with the above described binder resin according to the present invention.
- examples of such resins are described, for example, in Harumi Miyamoto and Hidehiko Takei, Imaging, Nos. 8 and 9 to 12, 1978 and Ryuji Kurita and Jiro Ishiwata, Kobunshi (Polymer), 17, 278-284 (1968).
- an olefin polymer an olefin copolymer, a vinyl chloride copolymer, a vinylidene chloride copolymer, a vinyl alkanoate polymer, a vinyl alkanoate copolymer, an allyl alkanoate polymer, an allyl alkanoate copolymer, a styrene and styrene derivative polymer, a styrene and styrene derivative copolymer, a butadiene-styrene copolymer, an isoprene-styrene copolymer, a butadiene-unsaturated carboxylic acid ester copolymer, an acrylonitrile copolymer, a methacrylonitrile copolymer, an alkyl vinyl ether copolymer, acrylic acid ester polymer and copolymer, a methacrylic acid ester polymer and copolymer,
- such resins are employed in a range of not more than 30% by weight based on the total weight of the binder resin.
- the ratio of the resin (A) or (A') to the resin (B) is not particularly restricted, but ranges preferably from 5 to 50/95 to 50 by weight, more preferably from 10 to 40/90 to 60 by weight.
- the inorganic photoconductive substance which can be used in the present invention includes zinc oxide, titanium oxide, zinc sulfide, cadmium sulfide, cadmium carbonate, zinc selenide, cadmium selenide, tellurium selenide, and lead sulfide, preferably zinc oxide.
- the resin binder is used in a total amount of from 10 to 100 parts by weight, preferably from 15 to 50 parts by weight, per 100 parts by weight of the inorganic photoconductive substance.
- various dyes can be used as spectral sensitizer in the present invention.
- the spectral sensitizers are carbonium dyes, diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, phthalein dyes, polymethine dyes (e.g., oxonol dyes, merocyanine dyes, cyanine dyes, rhodacyanine dyes, and styryl dyes), and phthalocyanine dyes (including metallized dyes).
- oxonol dyes e.g., oxonol dyes, merocyanine dyes, cyanine dyes, rhodacyanine dyes, and styryl dyes
- phthalocyanine dyes including metallized dyes
- carbonium dyes triphenylmethane dyes, xanthene dyes, and phthalein dyes are described, for example, in JP-B-51-452, JP-A-50-90334, JP-A 50-114227, JP-A-53-39130, JP-A-53-82353, U.S. Pat. Nos. 3,052,540 and 4,054,450, and JP-A-57-16456.
- the polymethine dyes such as oxonol dyes, merocyanine dyes, cyanine dyes, and rhodacyanine dyes, include those described, for example, in F. M. Hammer, The Cyanine Dyes and Related Compounds. Specific examples include those described, for example, in U.S. Pat. Nos. 3,047,384, 3,110,591, 3,121,008, 3,125,447, 3,128,179, 3,132,942, and 3,622,317, British Patents 1,226,892, 1,309,274 and 1,405,898, JP-B-48-7814 and JP-B-55-18892.
- polymethine dyes capable of spectrally sensitizing in the longer wavelength region of 700 nm or more, i.e., from the near infrared region to the infrared region include those described, for example, in JP-A-47-840, JP-A-47-44180, JP-B-51-41061, JP-A-49-5034, JP-A-49-45122, JP-A-57-46245, JP-A-56-35141, JP-A-57-157254, JP-A-61-26044, JP-A-61-27551, U.S. Pat. Nos. 3,619,154 and 4,175,956, and Research disclosure, 216, 117 to 118 (1982).
- the light-sensitive material of the present invention is particularly excellent in that the performance properties are not liable to variation even when combined with various kinds of sensitizing dyes.
- the photoconductive layer may further contain various additives commonly employed in conventional electrophotographic light-sensitive layer, such as chemical sensitizers.
- additives include electron-accepting compounds (e.g., halogen, benzoquinone, chloranil, acid anhydrides, and organic carboxylic acids) as described in the above-mentioned Imaging, 1973, No. 8, 12; and polyarylalkane compounds, hindered phenol compounds, and p-phenylenediamine compounds as described in Hiroshi Kokado et al., Saikin-no Kododen Zairyo to Kankotai no Kaihatsu Jitsuyoka, Chaps. 4 to 6, Nippon Kagaku Joho K. K. (1986).
- electron-accepting compounds e.g., halogen, benzoquinone, chloranil, acid anhydrides, and organic carboxylic acids
- polyarylalkane compounds hindered phenol compounds
- p-phenylenediamine compounds
- the amount of these additives is not particularly restricted and usually ranges from 0.0001 to 2.0 parts by weight per 100 parts by weight of the photoconductive substance.
- the photoconductive layer suitably has a thickness of from 1 to 100 ⁇ m, preferably from 10 to 50 ⁇ m.
- the thickness of the charge generating layer suitably ranges from 0.01 to 1 ⁇ m, particularly from 0.05 to 0.5 ⁇ m.
- an insulating layer can be provided on the light-sensitive layer of the present invention.
- the insulating layer is made to serve for the main purposes for protection and improvement of durability and dark decay characteristics of the light-sensitive material, its thickness is relatively small.
- the insulating layer is formed to provide the light-sensitive material suitable for application to special electrophotographic processes, its thickness is relatively large, usually ranging from 5 to 70 ⁇ m, particularly from 10 to 50 ⁇ m.
- Charge transporting material in the above-described laminated light-sensitive material include polyvinylcarbazole, oxazole dyes, pyrazoline dyes, and triphenylmethane dyes.
- the thickness of the charge transporting layer ranges from 5 to 40 ⁇ m, preferably from 10 to 30 ⁇ m.
- Resins to be used in the insulating layer or charge transporting layer typically include thermoplastic and thermosetting resins, e.g., polystyrene resins, polyester resins, cellulose resins, polyether resins, vinyl chloride resins, vinyl acetate resins, vinyl chloride-vinyl acetate copolymer resins, polyacrylate resins, polyolefin resins, urethane resins, epoxy resins, melamine resins, and silicone resins.
- thermoplastic and thermosetting resins e.g., polystyrene resins, polyester resins, cellulose resins, polyether resins, vinyl chloride resins, vinyl acetate resins, vinyl chloride-vinyl acetate copolymer resins, polyacrylate resins, polyolefin resins, urethane resins, epoxy resins, melamine resins, and silicone resins.
- the photoconductive layer according to the present invention can be provided on any known support.
- a support for an electrophotographic light-sensitive layer is preferably electrically conductive.
- Any of conventionally employed conductive supports may be utilized in the present invention.
- Examples of usable conductive supports include a substrate (e.g., a metal sheet, paper, and a plastic sheet) having been rendered electrically conductive by, for example, impregnating with a low resistant substance; the above-described substrate with the back side thereof (opposite to the light-sensitive layer side) being rendered conductive and having further coated thereon at least one layer for the purpose of prevention of curling; the above-described substrate having provided thereon a water-resistant adhesive layer; the above-described substrate having provided thereon at least one precoat layer; and paper laminated with a conductive plastic film on which aluminum is vapor deposited.
- conductive supports and materials for imparting conductivity are described, for example, in Yukio Sakamoto, Denshishashin, 14, No. 1, pp. 2 to 11 (1975), Hiroyuki Moriga, Nyumon Tokushushi no Kagaku, Kobunshi Kankokai (1975), and M. F. Hoover, J, Macromol. Sci. Chem., A-4(6), pp. 1327 to 1417 (1970).
- a mixed solution of 95 g of methyl methacrylate, 5 g of thioglycolic acid, and 200 g of toluene was heated to 70° C. with stirring under a nitrogen gas stream and, after adding thereto 1.5 g of 4,4'-azobis(4-cyanovaleric acid) (hereinafter referred to as A.C.V.), the reaction was carried out for 8 hours. Then, to the reaction mixture were added 8 g of glycidyl methacrylate, 1.0 g of N,N-dimethyldodecylamine, and 0.5 g of t-butylhydroquinone, and the resulting mixture was stirred for 12 hours at 100° C. After cooling, the reaction mixture was reprecipitated from 2 liters of methanol to obtain 82 g of the polymer as a white powder. The weight average molecular weight (Mw) of the polymer was 5,800.
- a mixed solution of 95 g of 2-chlorophenyl methacrylate, 5 g of thioglycolic acid, and 200 g of toluene was heated to 70° C. with stirring under a nitrogen gas stream and, after adding thereto 1.5 g of 2,2'-azobis(isobutyronitrile) (hereinafter, A.I.B.N.), the reaction mixture were added 7.5 g of glycidyl methacrylate, 1.0 g of N,N-dimethyldodecylamine, and 0.8 g of t-butylhydroquinone, and the resulting mixture was stirred for 12 hours at 100° C. After cooling, the reaction mixture was reprecipitated from 2 liters of methanol to obtain 85 g of the polymer as a colorless transparent viscous product. Mw of the polymer was 3,500.
- a mixed solution of 94 g of butyl methacrylate, 6 g of 2-mercaptoethanol, and 200 g of toluene was heated to 70° C. with stirring under a nitrogen gas stream and, after adding thereto 1.2 g of A.I.B.N., the reaction was carried out for 8 hours.
- reaction mixture was cooled to 20° C. in a water bath and, after adding thereto 10.2 g of triethylamine, 14.5 g of methacrylic acid chloride was added dropwise to the reaction mixture with stirring for one hour. The resulting mixture was further stirred for one hour at that temperature. Thereafter, 0.5 g of t-butylhydroquinone was added thereto, and the mixture was stirred for 4 hours at 60° C. After cooling, the reaction product was reprecipitated to obtain 79 g of the polymer as a colorless transparent viscous product. Mw of the product was 6,000.
- a mixed solution of 95 g of ethyl methacrylate and 200 g of toluene was heated to 70° C. with stirring under a nitrogen gas stream and, after adding thereto 5 g of 2,2'-azobis(cyanoheptanol), the reaction was carried out for 8 hours.
- reaction mixture was cooled to 20° C. in a water bath and, after adding thereto 1.0 g of triethylamine and 21 g of methacrylic acid anhydride followed by stirring for one hour, the resulting mixture was stirred for 6 hours at 60° C.
- reaction product obtained was reprecipitated from 2 liters of methanol to obtain 75 g of the polymer as a colorless transparent viscous product. Mw of the product was 8,500.
- a mixed solution of 96 g of 2-chloro-6-methylphenyl methacrylate, 4 g of thioglycolic acid and 200 g of toluene was heated to 75° C. with stirring under a nitrogen gas stream and, after adding thereto 1.5 g of A.I.B.N., the reaction was carried out for 8 hours. Then, the reaction mixture was cooled to 25° C. and, after adding thereto 10 g of 2-hydroxyethyl methacrylate and 1.5 g of t-butylhydroquinone, the resulting mixture was stirred.
- the crystals thus precipitated were removed by suction filtration, and the residue was reprecipitated from 2 liters of methanol.
- the precipitate thus formed was collected by decantation and dissolved in 200 ml of methylene chloride, and the solution was reprecipitated again from one liter of methanol.
- the precipitate thus formed was collected by decantation and dried under reduced pressure.
- the amount of the liquid product obtained was 58 g. Mw was 7.3 ⁇ 10 3 .
- a mixed solution of 75 g of benzyl methacrylate, 25 g of macromonomer (MM-1), 4 g of thiosalicylic acid, and 150 g of toluene was heated to 75° C. with stirring under a nitrogen gas stream and, after adding thereto 1.0 g of A.I.B.N., the reaction was carried out for 4 hours. Then, 0.5 g of A.I.B.N. was added thereto, and the reaction was carried out for 3 hours. After further adding thereto 0.3 g of A.I.B.N., the reaction was carried out for 3 hours.
- Mw of the copolymer obtained was 8.8 ⁇ 10 3 .
- a mixed solution of 70 g of 2-bromophenyl methacrylate, 30 g of macromonomer (MM-2), 100 g of toluene, and 50 g of isopropanol was heated to 80° C. with stirring under a nitrogen gas stream and, after adding thereto 5.0 g of A.C.V., the reaction was carried out for 6 hours. Then; 1.0 g of A.C.V. was added thereto, and the reaction was carried out for 4 hours.
- Mw of the copolymer obtained was 8.8 ⁇ 10 4 .
- a mixed solution of 85 g of phenyl methacrylate, 15 g of macromonomer (MM-6) having the structure shown below, and 200 g of tetrahydrofuran was heated to 75° C. with stirring under a nitrogen gas stream and, after adding thereto 5 g of A.C.C., the reaction was carried out for 4 hours. Then, 1.0 g of A.C.C. was further added thereto, and the reaction was carried out for 3 hours.
- the reaction mixture was cooled to 25° C. and, after adding thereto 12 g of pyridine, 100 g of a dimethylformamide solution of 15 g of 11-aminododecanoic acid was added dropwise to the mixture with stirring over a period of one hour. The mixture was stirred for 2 hours as it was and further stirred for one hour at 40° C. After cooling, the reaction product was reprecipitated from 2 liters of methanol, the white powder thus formed was collected by filtration, and dissolved in 100 g of tetrahydrofuran. The solution was reprecipitated from one liter of methanol, and a white powder formed was collected by filtration. After drying under reduced pressure, 48 g of the product was obtained as a white powder. Mw was 8.5 ⁇ 10 3 . ##STR110##
- the resin (A-16) is shown below: ##STR111##
- the range of Mw of the copolymers obtained was from 8 ⁇ 10 3 to 9.5 ⁇ 10 3 .
- a mixed solution of 90 g of ethyl methacrylate, 10 g of 2-hydroxyethyl methacrylate, 5 g of thioglycolic acid, and 200 g of toluene was heated to 75° C. with stirring under a nitrogen gas stream and, after adding thereto 1.0 g of 2,2-azobisisobutyronitrile (A.I.B.N.), the reaction was carried out for 8 hours. Then, to the reaction mixture were added 8 g of glycidyl, methacrylate, 1.0 g of N,N-dimethyldodecylamine, and 0.5 g of t-butylhydroquinone, and the resulting mixture was stirred for 12 hours at 100° C. After cooling, the reaction mixture was reprecipitated from 2 liters of n-hexane to obtain 82 g of a white powder. Mw of the polymer (MM'-1) was 3.8 ⁇ 10 3 . ##STR125##
- a mixed solution of 90 g of butyl methacrylate, 10 g of methacrylic acid, 4 g of 2-mercaptoethanol, and 200 g of tetrahydrofuran was heated to 70° C. with stirring under a nitrogen gas stream and, after adding thereto 1.2 g of A.I.B.N., the reaction was carried out for 8 hours.
- reaction mixture was cooled to 20° C. in a water bath and, after adding thereto 10.2 g of triethylamine, 14.5 g of methacrylic acid chloride was added dropwise to the mixture with stirring at a temperature of lower than 25° C. Thereafter, the mixture was further stirred for one hour. Then, 0.5 g of t-butylhydroquinone was added to the mixture, and the resulting mixture was stirred for 4 hours at 60° C.
- reaction mixture was added dropwise to one liter of water with stirring (over a period of about 10 minutes) followed by stirring for one hour. After allowing to stand the mixture, water was removed by decantation. After washing twice with water, the reaction mixture was dissolved in 100 ml of tetrahydrofuran and the solution was reprecipitated from petroleum ether. The precipitates thus formed were collected by decantation and dried under reduced pressure to obtain 65 g of the Product (MM'-2) as a viscous product Mw of the polymer was 5.6 ⁇ 10 3 . ##STR126##
- a mixed solution of 95 g of benzyl methacrylate, 5 g of 2-phosphonoethyl methacrylate, 4 g of 2-aminoethylmercaptan, and 200 g of tetrahydrofuran was heated to 70° C. with stirring under a nitrogen gas stream. Then, after adding thereto 1.5 g of A.I.B.N., the reaction was carried out for 4 hours and, after further adding thereto 0.5 g of A.I.B.N., the reaction was carried out for 4 hour.
- reaction mixture was cooled to 20° C. and after adding thereto 10 g of acrylic anhydride, the resulting mixture was stirred for one hour at a temperature of from 20° to 25° C. Then, 1.0 g of t-butylhydroquinone was added to the mixture, followed by stirring for 4 hours at a temperature of from 50° to 60° C. After cooling, the reaction mixture was added dropwise to one liter of water with stirring followed by stirring for one hour and, after allowing the reaction mixture to stand, water was removed by decantation. After repeatedly washing the mixture twice with water, the reaction mixture was reprecipitated from 2 liters of petroleum ether.
- a mixed solution of 90 g of 2-chlorophenyl methacrylate, 10 g of the monomer having the formula (I') shown below, 4 g of thioglycolic acid, and 200 g of toluene was heated to 70° C. with stirring under a nitrogen gas stream. After adding thereto 1.5 g of A.I.B.N., the reaction was carried out for 5 hours and, after further adding thereto 0.5 g of A.I.B.N., the reaction was carried out for 4 hour.
- reaction was carried out for 8, hours at 110° C. After cooling, the reaction mixture was added to a mixture of 3 g of p-toluenesulfonic acid and 100 ml of an aqueous solution of 90% by volume tetrahydrofuran followed by stirring for one hour at a temperature of from 30° to 35° C. The reaction mixture was reprecipitated from 2 liters of a water/methanol (1/3 by volume) mixed solution, and the precipitates formed were collected by decantation.
- a mixed solution of 95 g of 2,6-dichlorophenyl methacrylate, 5 g of 3-(2'-nitrobenzyloxysulfonyl)propyl methacrylate, 150 g of toluene, and 50 g of isopropyl alcohol was heated to 80° C. with stirring under a nitrogen gas stream. Then, after adding thereto 5.0 g of 2,2'-azobis(2-cyanovaleric acid) (A.C.V.), the reaction was carried out for 5 hours and, after further adding thereto 1.0 g of A.C.V., the reaction was carried out for 4 hours.
- reaction mixture was reprecipitated from 2 liters of methanol, and the powder formed was collected by filtration and dried under reduced pressure.
- the mixture was irradiated by a high-pressure mercury lamp of 80 W for one hour. Thereafter, the reaction mixture was reprecipitated from one liter of methanol, and the powder formed was collected by filtration and dried under reduced pressure to obtain 34 g of the polymer (MM'-5).
- a mixed solution of 75 g of phenyl methacrylate, 25 g of the compound (MM'-2) obtained in Synthesis Example 2 of Macromonomer (MA'), and 100 g of toluene was heated to 100° C. with stirring under a nitrogen gas stream.
- a mixed solution of 70 g of 2-chlorophenyl methacrylate, 30 g of the compound (MM'-1) obtained in Synthesis Example 1 of Macromonomer (MA'), 3.0 g of ⁇ -mercaptopropionic acid, and 150 g of toluene was heated to 80° C. with stirring under a nitrogen gas stream. After adding thereto 1.0 g of A.I.B.N., the reaction was carried out for 4 hours. After further adding thereto 0.5 g of A.I.B.N., the reaction was carried out for 2 hours, and after further adding thereto 0.3 g of A.I.B.N., the reaction was carried out for 3 hours to obtain a copolymer (A'-2). Mw of the copolymer was 8.5 ⁇ 10 3 . ##STR131##
- a mixed solution of 60 g of 2-chloro-6-methylphenyl methacrylate, 25 g of the compound (MM'-4) obtained in Synthesis Example 4 of Macromonomer (MA'), 15 g of methyl acrylate, 100 g of toluene, and 50 g of isopropyl alcohol was heated to 80° C. with stirring under a nitrogen gas stream. After adding thereto 5 g of A.C.V., the reaction was carried out for 5 hours and, after further adding thereto 1 g of A.C.V., the reaction was carried out for 4 hours, to obtain a copolymer (A'-3).
- each of resins (A') shown in Table 3 was prepared.
- the range of Mw of the copolymers obtained was from 6.0 ⁇ 10 3 to 9 ⁇ 10 3 .
- Mw of the copolymers obtained was in the range of from 5 ⁇ 10 3 to 9 ⁇ 10 3 .
- a mixed solution of 10 g of triphenylmethyl methacrylate, and 100 g of toluene was sufficiently degassed in a nitrogen stream and cooled to -20° C. Then, 0.02 g of 1,1-diphenylbutyl lithium was added to the mixture, and the reaction was conducted for 10 hours.
- a mixed solution of 90 g of ethyl methacrylate and 100 g of toluene was sufficiently degassed in a nitrogen stream and the resulting mixed solution was added to the above described mixture, and then reaction was further conducted for 10 hours.
- the reaction mixture was adjusted to 0° C., and carbon dioxide gas was passed through the mixture in a flow rate of 60 ml/min for 30 minutes, then the polymerization reaction was terminated.
- the temperature of the reaction solution obtained was raised to 25° C. under stirring, 6 g of 2-hydroxyethyl methacrylate was added thereto, then a mixed solution of 10 g of dicyclohexylcarbodiimide, 0.2 g of 4-N,N-dimethylaminopyridine and 30 g of methylene chloride was added dropwise thereto over a period of 30 minutes, and the mixture was stirred for 3 hours.
- a mixed solution of 5 g of benzyl methacrylate, 0.01 g of (tetraphenyl porphynate) aluminum methyl, and 60 g of methylene chloride was raised to a temperature of 30° C. in a nitrogen stream.
- the mixture was irradiated with light from a xenon lamp of 300 W at a distance of 25 cm through a glass filter, and the reaction was conducted for 12 hours.
- To the mixture was further added 45 g of butyl methacrylate, after similarly light-irradiating for 8 hours, 5 g of 4-bromomethylstyrene was added to the reaction mixture followed by stirring for 30 minutes, then the reaction was terminated. Then, Pd-C was added to the reaction mixture, and a catalytic reduction reaction was conducted for one hour at 25° C.
- a mixed solution of 20 g of 4-vinylphenyloxytrimethylsilane and 100 g of toluene was sufficiently degassed in a nitrogen stream and cooled to 0° C. Then, 0.1 g of 1,1-diphenyl-3-methylpentyl lithium was added to the mixture followed by stirring for 6 hours.
- a mixed solution of 80 g of 2-chloro-6-methylphenyl methacrylate and 100 g of toluene was sufficiently degassed in a nitrogen stream and the resulting mixed solution was added to the above described mixture, and then reaction was further conducted for 8 hours.
- a mixed solution of 15 g of triphenylmethyl acrylate and 100 g of toluene was sufficiently degassed in a nitrogen stream and cooled to -20° C. Then, 0.1 g of sec-butyl lithium was added to the mixture, and the reaction was conducted for 10 hours.
- a mixed solution of 85 g of styrene and 100 g of toluene was sufficiently degassed in a nitrogen stream and the resulting mixed solution was added to the above described mixture, and then reaction was further conducted for 12 hours.
- the reaction mixture was adjusted to 0° C., 8 g of benzyl bromide was added thereto, and the reaction was conducted for one hour, followed by reacting at 25° C. for 2 hours.
- a mixed solution of 80 g of phenyl methacrylate and 4.8 g of benzyl N-hydroxyethyl-N-ethyldithiocarbamate was placed in a vessel in a nitrogen stream followed by closing the vessel and heated to 60° C.
- the mixture was irradiated with light from a high-pressure mercury lamp for 400 W at a distance of 10 cm through a glass filter for 10 hours to conduct a photopolymerization.
- a mixed solution of 80 g of ethyl methacrylate, 20 g of Macromonomer (M-1) and 150 g of toluene was heated at 65° C. in a nitrogen stream, and 0.8 g of 1,1-azobis(cyclohexane-1-carbonitrile (hereinafter, A.B.C. C.) was added thereto to effect reaction for 5 hours. Then, 0.5 g of A.B.C.C. was further added thereto, followed by reacting for 5 hours.
- the resulting copolymer shown below had an Mw of 1.0 ⁇ 10 5 . ##STR198##
- Resins (B) shown in Table 3 below were synthesized under the same polymerization conditions as described in Synthesis Example 2 of resin (B). Each of these resins had an Mw of from 7 ⁇ 10 4 to 9 ⁇ 10 4 .
- Resins (B) shown in Table 4 below were synthesized under the same polymerization conditions as described in Synthesis Example 1 of Resin (B). Each of these resins had an Mw of from 9 ⁇ 10 4 to 2 ⁇ 10 5 .
- the coating composition was coated on paper, which had been subjected to electrically conductive treatment, by a wire bar to a dry coverage of 18 g/m 2 , followed by drying at 110° C. for 30 seconds.
- the coated material was allowed to stand in a dark place at 20° C. and 65% RH (relative humidity) for 24 hours to prepare an electrophotographic light-sensitive material.
- An electrophotographic light-sensitive material was prepared by following the same procedure as Example 1 except that 6 g of resin (R-1) shown below was used in place of resin (A-1) and 34 g of poly(ethyl acrylate) (R-2) (Mw: 2.4 ⁇ 10 5 ) was used in place of 34 g of resin (B-1). ##STR226##
- An electrophotographic light-sensitive material was prepared by following the same procedure as Example 1 except that 40 g of resin (R-3) shown below was used in place of 5 g of resin (A-1) and 34 g of resin (B-3). ##STR227##
- Example 1 Each of the light-sensitive materials thus obtained in Example 1 and Comparative Examples A and B was evaluated for film properties in terms of surface smoothness and mechanical strength; electrostatic characteristics; image forming performance; oil-desensitivity when used as an offset master plate precursor (expressed in terms of contact angle of the layer with water after the oil-desensitization treatment); and printing suitability (expressed in terms of background stains and printing durability).
- Table 7 The results obtained are shown in Table 7 below.
- the smoothness (sec/cc) of light-sensitive material was measured using a Beck's smoothness test machine (manufactured by Kumagaya Riko K. K.) under an air volume condition of 1 cc.
- the surface of light-sensitive material was repeatedly rubbed 1,000 times with emery paper (#1000) under a load of 50 g/cm 2 using a Heidon 14 Model surface testing machine (manufactured by Shinto Kagaku K. K.). After removing abrasion dusts from the layer, the film retention (%) was determined from the weight loss of the photoconductive layer, which was referred to as the mechanical strength.
- the light-sensitive material was charged by applying thereto corona discharge of -6 kV for 20 seconds using a paper analyzer (Paper Analyzer Type SP-428, manufactured by Kawaguchi Denki K. K.) in a dark place under conditions of 20° C. and 65% RH. Then seconds after the corona discharge, the surface potential V 10 was measured. Then, the sample was allowed to stand for 180 seconds in a dark place and the potential V 190 was measured.
- the surface of the photoconductive layer was charged to -500 V by corona discharge, then irradiated by monochromatic light of a wavelength of 785 nm, the time required for decaying the surface potential (V 10 ) to 1/10 thereof was measured, and the exposure amount E 1/10 (erg/cm 2 ) was calculated therefrom.
- the surface of the photoconductive layer was charged to -500 V by corona discharge in the same manner as described for the measurement of E 1/10 , then irradiated by monochromatic light of a wavelength of 785 nm, the time required for decaying the surface potential (V 10 ) to 1/100 thereof was measured, and the exposure amount E 1/100 (erg/cm 2 ) was calculated therefrom.
- Condition I 20° C. and 65% RH
- Condition II 30° C. and 80% RH
- the light-sensitive material was allowed to stand for one day under Condition I or II. Then, under each of Conditions I and II the sample was charged to -5 kV, irradiated by scanning with a gallium-aluminum-arsenic semiconductor laser (oscillation wavelength: 780 nm) of 2.8 mW output as a light source in an exposure amount on the surface of 50 erg/cm 2 , at a pitch of 25 ⁇ m and a scanning speed of 300 m/sec., and then developed using ELP-T (made by Fuji Photo Film Co., Ltd.) as a liquid developer followed by fixing. The duplicated image thus obtained was visually evaluated for fog and image quality.
- the original used for the duplication was composed of letters by a word processor and a cutting of letters on straw paper pasted upon thereon.
- the light-sensitive material was passed once through an etching processor using an oil-desensitizing solution (ELP-EX, made by Fuji Photo Film Co., Ltd.) to desensitize the surface of the photoconductive layer. Then, a drop of 2 ⁇ l of distilled water was placed on the surface, and the contact angle formed between the surface and the water drop thereon was measured using a goniometer.
- ELP-EX oil-desensitizing solution
- the light-sensitive material was subjected to the plate making under the same conditions as described in *4) above to form a toner image, and the sample of the photoconductive layer was oil-desensitized under the same conditions as described in *5) above.
- the printing plate thus prepared was mounted on an offset printing machine (Oliver Model 52, manufactured by Sakurai Seisakusho K. K.) as an offset master plate following by printing.
- the number of prints obtained without causing background stains in the non-image portions of prints and problems on the quality of the image portions thereof was referred to as the printing durability. The larger the number of prints, the better the printing durability.
- the light-sensitive material according to the present invention had good surface smoothness and mechanical strength of the photoconductive layer, and good electrostatic characteristics.
- the duplicated image formed was clear and free from background fog in the non-image area. Those results appear to be due to sufficient adsorption of the binder resin onto the photoconductive substance and sufficient covering of the surface of the particles with the binder resin.
- oil-desensitization with an oil-desensitizing solution was sufficient to render the non-image areas satisfactorily hydrophilic, as shown by a small contact angle of 10° or less with water. On practical printing using the resulting printing plate, no background stains were observed in the prints.
- E 1/100 shows the potential remaining on the non-image portion (already exposed portion) after exposure at practical imaging or photographing and that the value is less shows that background staining does not occur at the non-image portions after development.
- the residual potential is lower than -10 V. That is, actually, it means a necessary exposure amount for lowering V R to lower than -10 V.
- a scanning exposure system by a semiconductor laser light it is very important for designing the optical system of a copying machine (the cost of the apparatus, accuracy of the optical path of the optical system, etc.) to lower V R to lower than -10 V with a small exposure amount.
- each of electrophotographic light-sensitive materials was prepared.
- the electrostatic characteristics shown in Table 8 were determined under the condition of 30° C. and 80% RH.
- each of the electrophotographic light-sensitive materials of the present invention was good in all the points of the smoothness of the photoconductive layer, the film strength, the electrostatic characteristics, and the printing property.
- each of electrophotographic light-sensitive materials was prepared.
- Each of the electrophotographic light-sensitive materials according to the present invention thus obtained was excellent in the charging property, the dark charge retentivity, and the light sensitivity and gave clear images having no background fog even under high-temperature and high-humidity severe conditions (30° C., 80% RH).
- the coating composition was coated on a paper which had been subjected an electrically conductive treatment, by a wire bar at a dry coverage of 25 g/m 2 and dried for 30 seconds at 110° C., and then allowed to stand in the dark for 24 hours under the condition of 20° C., 65% RH to obtain an electrophotographic light-sensitive material.
- the film-forming property surface smoothness
- the film strength the electrostatic characteristics and image-forming performance under the environmental conditions of 20° C., 65% RH and 30° C., 80% RH were determined.
- each of the light-sensitive materials was used as an offset master plate and the oil-desensitizing property (the contact angle of the photo-conductive layer after being desensitized with water) of the light-sensitive layer and the printing property (background stains, printing durability, etc.) were also determined.
- the potential decay at the unexposed portions (image portions) causes the reduction of image quality (e.g., the reduction of Dm, the occurrence of blurring of fine lines, letters, etc.) of actually reproduced images.
- image quality e.g., the reduction of Dm, the occurrence of blurring of fine lines, letters, etc.
- the semiconductor laser beam becomes low output and the amount of light irradiation is restricted, the residual potential after exposure is a serious problem and the residual potential appears as a background fog at non-image portions at actual image formation. This corresponds to E 1/100 of electrostatic characteristics and shows that the value is preferably smaller.
- the samples of the present invention provided more than 8,000 prints having clear image quality and having no background stains regardless of the environmental conditions in the case of making printing plate.
- the electrophotographic light-sensitive material of the present invention was excellent in the electrostatic characteristics and image-forming performance in Example 29 using the binder resin (A) having the polar group at the terminal of the main chain as compared with Example 28, and further the printing property as the offset master plate was excellent in Example 29.
- the electrophotographic light-sensitive materials .of the present invention are good in all the prints of the smoothness, the film strength, the electrostatic characteristics, and the printing property of the photoconductive layers.
- Example 28 By following the same procedure as Example 28 except that 6 g of each of the resins (A') shown in Table 11 and 34 g of each of the resins (B) shown in Table 11 were used in place of 6 g of the resin (A'-8) and 34 g of the resin (B-1) and also 0.018 g of cyanine dye (B) shown below was used in place of 0.018 g of the cyanine dye (A), each of electrophotographic light-sensitive materials was prepared.
- the samples of according to the present invention showed excellent results, and, when the resin (A') has the polar group at the terminal thereof, the electrostatic characteristics were further improved. Also, when the samples were used as offset master plate for printing, more than 8,000 prints having good image quality were obtained.
- Example 28 By following the same procedure as Example 28 except that 6 g of each of the resins (A') shown in Table 12 and 34 g of each of the resins (B) shown in Table were used in place of 6 g of the resin (A'-8) and 34 g of the resin (B-1) in Example 28 and also 0.016 g of methine dye (C) shown below was used in place of 0.018 g of the cyanine dye (A), each of the electrophotographic light-sensitive materials was prepared.
- Electrostatic characteristics of each of the samples were measured in the same manner as in Example 28.
- Each of the electrographic light-sensitive materials of the present invention was excellent in the charging property, dark charge retentivity, and light sensitivity and also at actual image formation under a high-temperature and high-humidity severe condition (30° C., 80% RH), clear images having no background fog were obtained.
- the coating composition was coated on a paper, which had been subjected to an electrically conductive treatment, by a wire bar at a dry coverage of 20 g/m 2 , dried for 30 minutes at 110° C., and allowed to stand in the dark for 24 hours under the condition of 20° C., 65% RH to obtain each of the electrophotographic light-sensitive materials.
- Electrostatic characteristics of the resulting samples were determined in the same manner as in Example 28 under the condition of 30° C., 80% RH.
- each of the electrophotographic light-sensitive materials of the present invention was excellent in the charging property, dark charge retentivity, and light sensitivity, and, at actual image formation, under the high-temperature and high-humidity severe condition (30° C., 80% RH), clear images having no background fog were obtained.
- E 1/10 in the electrophotographic characteristics shown in Table 13 was obtained as follows. That is, after charging the surface of each photoconductive layer to -400 V by corona discharging, the surface was irradiated by visible light at an illuminance of 2.0 lux, the time required to decay the surface potential (V 10 ) to 1/10, and from the time, the exposure amount E 1/10 (lux.sec.) was calculated.
- the printing plate as prepared from the electrophotographic light-sensitive material by an Automatic Plate Making Machine ELP 404 V (made by Fuji Photo Film Co., Ltd.) using ELP-T as a toner to form toner images.
- ELP 404 V made by Fuji Photo Film Co., Ltd.
- Example 62 By following the same procedure as Example 62 except that 6 g of each of the resins (A') shown in Table 14 below and 34 g of each of the resins (B) shown in Table 14 were used in place of 6.5 g of the resin (A'-1) and 33.5 g of the resin (B-1) in Example 62, each of electrophotographic light-sensitive materials was prepared.
- Each of the electrophotographic light-sensitive materials was excellent in the charging property, dark charge retentivity, and light sensitivity, and also at actual image formation under a high-temperature and high-humidity condition (30° C., 80% RH), clear images having no background fog were obtained.
- each sample was used as an offset master plate for printing, more than 8,000 prints having clear images and no background fog could be obtained.
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Abstract
Description
TABLE A __________________________________________________________________________ Moiety A Moiety B Moiety C __________________________________________________________________________ ##STR63## COOH, NH.sub.2 OH ##STR64## COCl, Acid Anhydride OH, NH.sub.2 COOH, SO.sub.3 H, PO.sub.3 H.sub.2, SO.sub.2 Cl, ##STR65## COOH, NHR.sub.15 Halogen COOH, SO.sub.3 H, PO.sub.3 H.sub.2, (wherein R.sub.15 is a hydrogen atom or an alkyl group) ##STR66## COOH, NHR.sub.15 ##STR67## OH ##STR68## OH, NHR.sub.15 COCl, SO.sub.2 Cl COOH, SO.sub.3 H, PO.sub.3 H.sub.2 __________________________________________________________________________
TABLE 1 ##STR78## Production Example of Resin (A) Resin (A) W R T R x/y 3 A-3 HOOCCH.sub.2 C.sub.2 H.sub.5 ##STR79## ##STR80## 60/40 4 A-4 HOOC(CH.sub.2 ).sub.2 ##STR81## ##STR82## C.sub.3 H.sub.7 80/20 5 A-5 ##STR83## CH.sub.2 C.sub.6 H.sub.5 ##STR84## CH.sub.2 C.sub.6 H.sub.5 70/30 6 A-6 ##STR85## ##STR86## ##STR87## C.sub.2 H.sub.5 80/20 7 A-7 ##STR88## ##STR89## " C.sub.4 H.sub.9 70/30 8 A-8 ##STR90## CH.sub.3 ##STR91## CH.sub.2 C.sub.6 H.sub.5 70/30 9 A-9 ##STR92## ##STR93## ##STR94## CH.sub.3 80/20 10 A-10 ##STR95## ##STR96## ##STR97## ##STR98## 80/20 11 A-11 HOOC(CH.sub.2).sub.2 COO(CH.sub.2).sub.2 ##STR99## " CH.sub.2 C.sub.6 H.sub.5 75/25 12 A-12 ##STR100## CH.sub.2 CH.sub.2 OC.sub.6 H.sub.5 " ##STR101## 50/50 13 A-13 ##STR102## ##STR103## ##STR104## C.sub.2 H.sub. 5 80/20 14 A-14 HOOCCH.sub.2 ##STR105## ##STR106## " 80/20 15 A-15 ##STR107## ##STR108## ##STR109## C.sub.6 H.sub.5 75/25
TABLE 2 __________________________________________________________________________ ##STR112## Production Example of Resin (A) Resin (A) R Y x/y __________________________________________________________________________ 17 A-17 ##STR113## ##STR114## 85/15 18 A-18 ##STR115## ##STR116## 90/10 19 A-19 ##STR117## ##STR118## 85/15 20 A-20 C.sub.2 H.sub.5 ##STR119## 70/30 21 A-21 CH.sub.2 C.sub.6 H.sub.5 ##STR120## 60/40 22 A-22 C.sub.2 H.sub.5 ##STR121## 75/25 23 A-23 C.sub.6 H.sub.5 ##STR122## 80/20 24 A-24 ##STR123## ##STR124## 75/25 __________________________________________________________________________
TABLE 3 __________________________________________________________________________ ##STR133## Production Resin x/y Example (A) R R' (weight ratio) Y __________________________________________________________________________ 4 A-4 C.sub.2 H.sub.5 ##STR134## 90/10 ##STR135## 5 A-5 C.sub.3 H.sub.7 ##STR136## 85/15 ##STR137## 6 A-6 C.sub.4 H.sub.9 ##STR138## 90/10 ##STR139## 7 A-7 ##STR140## CH.sub.3 90/10 ##STR141## 8 A-8 ##STR142## C.sub.2 H.sub.5 90/10 ##STR143## 9 A-9 ##STR144## C.sub.4 H.sub.9 92/8 ##STR145## 10 A-10 CH.sub.3 ##STR146## 93/7 ##STR147## 11 A-11 CH.sub.3 C.sub.2 H.sub.5 90/10 ##STR148## 12 A-12 ##STR149## C.sub.2 H.sub.5 95/5 ##STR150## 13 A-13 ##STR151## ##STR152## 90/10 ##STR153## __________________________________________________________________________
TABLE 4 ##STR154## Resin (A) W R R' x/y (weight ratio) Y A-14 HOOCH.sub.2 CS ##STR155## C.sub.2 H.sub.5 90/10 ##STR156## A-15 ##STR157## ##STR158## ##STR159## 85/15 ##STR160## A-16 ##STR161## ##STR162## ##STR163## 90/10 ##STR164## A-17 ##STR165## C.sub.2 H.sub.5 ##STR166## 92/8 ##STR167## A-18 HO.sub.3 SCH.sub.2 CH.sub.2 S ##STR168## C.sub.4 H.sub.9 93/7 ##STR169## A-19 HOCH.sub.2 CH.sub.2S ##STR170## C.sub.2 H.sub.5 92/8 ##STR171## A-20 HOOC(CH.sub.2).sub.2 S ##STR172## C.sub.3 H.sub.7 95/5 ##STR173## A-21 ##STR174## ##STR175## ##STR176## 80/20 ##STR177## A-22 HOOC(CH.sub.2).sub.2 S ##STR178## C.sub.2 H.sub.5 90/10 ##STR179## A-23 ##STR180## ##STR181## C.sub.3 H.sub.7 90/10 ##STR182## A-24 " ##STR183## ##STR184## 90/10 ##STR185## A-25 " ##STR186## CH.sub.2 C.sub.6 H.sub.5 85/15 ##STR187## A-26 HOOC(CH.sub.2).sub.2 S ##STR188## C.sub.4 H.sub.9 95/5 ##STR189## A-27 " ##STR190## ##STR191## 95/5 ##STR192##
TABLE 5 ##STR200## Synthesis Example Resin [B] R X' x/y b.sub.1 /b.sub.2 R' Z' y'/z' 3 B-3 CH.sub.3 COO(CH.sub.2).sub.2 OOC 90/10 CH.sub.3 /CH.sub.3 COOC.sub.4 H.sub.9 ##STR201## 90/10 4 B-4 C.sub.3 H.sub.7 (n) ##STR202## 80/20 H/CH.sub.3 COOC.sub.2 H.sub.5 ##STR203## 80/20 5 B-5 CH.sub.2 H.sub.6 H.sub.5 COO(CH.sub.2).sub.2 90/10 H/CH.sub.3 OC.sub.2 H.sub.5 ##STR204## 95/5 6 B-6 C.sub.2 H.sub.5 COO 90/10 CH.sub.3 /CH.sub.3 COOC.sub.2 H.sub.5 ##STR205## 90/10 7 B-7 " COO(CH.sub.2).sub.2 NHCOO(CH.sub.2 ).sub.2 90/10 CH.sub.3 /H COOC.sub.3 H.sub.7 ##STR206## 85/15 8 B-8 CH.sub.2 C.sub.6 H.sub.5 ##STR207## 90/10 H/CH.sub.3 COOC.sub.2 H.sub.5 ##STR208## 92/8 9 B-9 C.sub.2 H.sub.5 COO 85/15 H/H ##STR209## ##STR210## 90/10
TABLE 6 __________________________________________________________________________ ##STR211## Synthesis Example No. Resin [B] R Y x/y __________________________________________________________________________ 10 B-10 C.sub.2 H.sub.5 ##STR212## 70/20 11 B-11 CH.sub.3 ##STR213## 75/15 12 B-12 C.sub.4 H.sub.9 ##STR214## 70/20 13 B-13 " ##STR215## 80/10 14 B-14 C.sub.4 H.sub.9 ##STR216## 75/15 15 B-15 CH.sub.2 C.sub.6 H.sub.5 ##STR217## 80/10 16 B-16 C.sub.2 H.sub.5 ##STR218## 85/5 17 B-17 C.sub.2 H.sub.5 ##STR219## 85/5 18 B-18 C.sub.2 H.sub.5 ##STR220## 75/15 19 B-19 ##STR221## ##STR222## 70/20 20 B-20 ##STR223## ##STR224## 70/20 __________________________________________________________________________
TABLE 7 ______________________________________ Comparative Comparative Example 1 Example A Example B ______________________________________ Surface Smooth- 220 210 220 ness*.sup.1) (sec/cc) Mechanical 98 90 96 Strength*.sup.2) (%) Electrostatic Characteristics*.sup.3) : V10 (-V): Condition I 555 550 560 Condition II: 550 540 500 DRR (%) Condition I 78 68 56 Condition II 75 60 30 E.sub.1/10 (erg/cm.sup.2): Condition I 28 40 100 Condition II 25 45 200 or more E.sub.1/100 (erg/cm.sup.2): Condition I 47 48 200 or more Condition II 49 110 200 or more Image-Forming Performance*.sup.4) : Condition I Good Background fog Dm not repro- slightly duced, fine lines formed. and letters cut out. Condition II Good Fine lines and Image cannot letters cut out. be distinguished from back- ground fog. Contact Angle*.sup.5) 10 or less 10 or less Greatly varied with Water (°): between 15 and 30°. Printing 10,000 8,000 prints Background Durability*.sup.6) : prints stains from the or more start of printing. ______________________________________ The evaluations described in Table 5 above were conducted as follows. *.sup.1) Smoothness of Photoconductive Layer: The smoothness (sec/cc) of lightsensitive material was measured using a Beck's smoothness test machine (manufactured by Kumagaya Riko K.K.) under an air volume conditio of 1 cc. *.sup.2) Mechanical Strength of Photoconductive Layer: The surface of lightsensitive material was repeatedly rubbed 1,000 times with emery pape (#1000) under a load of 50 g/cm.sup.2 using a Heidon 14 Model surface testing machine (manufactured by Shinto Kagaku K.K.). After removing abrasion dusts from the layer, the film retention (%) was determined from the weight loss of the photoconductive layer, which was referred to as th mechanical strength. *.sup.3) Electrostatic Characteristics: The lightsensitive material was charged by applying thereto corona discharge of -6 kV for 20 seconds usin a paper analyzer (Paper Analyzer Type SP428, manufactured by Kawaguchi Denki K.K.) in a dark place under conditions of 20° C. and 65% RH. Then seconds after the corona discharge, the surface potential V.sub.10 was measured. Then, the sample was allowed to stand for 180 seconds in a dark place and the potential V.sub.190 was measured. The dark decay retention rate (DRR (%)), i.e., the percent retention of potential after decaying for 180 seconds in a dark place, was calculated from the following equation: DRR (%) = (V.sub.190 /V.sub.10) × 100 (%). Also, the surface of the photoconductive layer was charged to -500 V by corona discharge, then irradiated by monochromatic light of a wavelength of 785 nm, the time required for decaying the surface potential (V.sub.10 to 1/10 thereof was measured, and the exposure amount E.sub.1/10 (erg/cm.sup.2) was calculated therefrom. Further, the surface of the photoconductive layer was charged to -500 V b corona discharge in the same manner as described for the measurement of E.sub.1/10, then irradiated by monochromatic light of a wavelength of 785 nm, the time required for decaying the surface potential (V.sub.10) to 1/100 thereof was measured, and the exposure amount E.sub.1/100 (erg/cm.sup.2) was calculated therefrom. The measurements were conducted under conditions of 20° C. and 65% RH (hereinafter referred to as Condition I) or 30° C. and 80% RH (hereinafter referred to as Condition II). *.sup.4) Image Forming Performance: The lightsensitive material was allowed to stand for one day under Condition I or II. Then, under each of Conditions I and II the sample was charged to -5 kV, irradiated by scanning with a galliumaluminum-arsenic semiconductor laser (oscillation wavelength: 780 nm) of 2.8 mW output as a light source in an exposure amount on the surface of 50 erg/cm.sup.2, at a pitch of 25 μm and a scanning speed of 300 m/sec., and then developed using ELP T (made by Fuj Photo Film Co., Ltd.) as a liquid developer followed by fixing. The duplicated image thus obtained was visually evaluated for fog and image quality. The original used for the duplication was composed of letters by a word processor and a cutting of letters on straw paper pasted upon thereon. *.sup.5) Contact Angle with Water: The lightsensitive material was passed once through an etching processor using an oildesensitizing solution (ELPEX, made by Fuji Photo Film Co., Ltd.) to desensitize the surface of the photoconductive layer. Then, a drop of 2 μl of distilled water was placed on the surface and the contact angle formed between the surface an the water drop thereon was measured using a goniometer. *.sup.6) Printing Durability: The lightsensitive material was subjected t the plate making under the same conditions as described in *.sup.4) above to form a toner image, and the sample of the photoconductive layer was oildesensitized under the same conditions as described in *.sup.5) above. The printing plate thus prepared was mounted on an offset printing machin (Oliver Model 52, manufactured by Sakurai Seisakusho K.K.) as an offset master plate following by printing. The number of prints obtained without causing background stains in the nonimage portions of prints and problems on the quality of the image portions thereof was referred to as the printing durability. The larger the number of prints, the better the printing durability.
TABLE 8 ______________________________________ E.sub.1/10 E.sub.1/100 Example Resin Resin V.sub.10 D.R.R. (erg/ (erg/ No. (A) (B) (-V) (%) cm.sup.2) cm.sup.2) ______________________________________ 2 A-3 B-3 540 70 35 57 3 A-5 B-5 550 76 28 50 4 A-8 B-10 540 73 35 56 5 A-18 B-8 550 80 20 40 6 A-22 B-12 540 70 36 55 7 A-23 B-10 550 79 25 43 8 A-6 B-8 610 85 18 35 9 A-7 B-13 550 80 23 38 10 A-9 B-14 560 82 20 37 11 A-11 B-9 550 84 18 33 12 A-14 B-16 600 85 17 32 13 A-16 B-11 550 77 27 49 14 A-17 B-15 605 83 18 34 15 A-19 B-4 540 78 28 42 16 A-21 B-20 545 75 30 48 17 A-24 B-19 540 75 32 48 ______________________________________
TABLE 9 __________________________________________________________________________ Dye (II) ##STR228## Example Resin (A) Resin (B) __________________________________________________________________________ 18 A-1 B-2 19 A-2 B-5 20 A-7 B-6 21 A-8 B-7 22 A-9 B-9 23 A-11 B-10 24 A-12 B-12 25 A-13 B-16 26 A-20 B-18 27 A-22 B-19 __________________________________________________________________________
TABLE 10 ______________________________________ Example Example Comparative Comparative 28 29 Example C Example D ______________________________________ Surface 530 500 500 510 Smoothness (sec/cc) Mechanical 96 95 82 85 Strength (%) Electrostatic Character- istics: V10 (-V): Condition I 560 640 490 505 Condition II 550 630 450 490 DRR (%) Condition I 83 88 75 77 Condition II 80 85 63 70 E.sub.1/10 (erg/cm.sup.2): Condition I 30 16 57 50 Condition II 27 18 48 47 E.sub.1/100 (erg/cm.sup.2): Condition I 48 30 86 90 Condition II 50 32 88 93 Image- Forming Performance: Condition I Good Good Dm slightly Dm lowered. lowered. Condition II Good Good Dm lowered. Dm lowered. Fine lines Fine lines and letters blurred. blurred. Contact 10 or less 10 or less 10 or less 10 or less Angle with Water (°): Printing 8,000 8,000 3,000 Fine lines Durability: prints prints prints cut out. ______________________________________
TABLE 11 __________________________________________________________________________ Cyanine Dye (B): ##STR232## Electrostatic Charac- Film teristics (30° C. 80% RH) Example Resin Resin Strength V.sub.10 D.R.R. E.sub.1/10 No. (A') (B) (%) (V) (%) (erg/cm.sup.2) __________________________________________________________________________ 30 A'-2 B-1 95 575 88 21 31 A'-4 B-2 90 540 80 32 32 A'-7 B-3 96 555 84 26 33 A'-8 B-4 93 550 82 27 34 A'-9 B-5 93 555 83 30 35 A'-11 B-6 93 545 79 30 36 A'-12 B-7 92 560 36 20 37 A'-13 B-8 91 555 86 19 38 A'-14 B-9 93 560 86 20 39 A'-16 B-10 92 570 87 20 40 A'-17 B-11 95 540 80 28 41 A'-18 B-12 96 550 83 26 42 A'-19 B-13 97 550 82 25 43 A'-20 B-14 95 550 83 21 44 A'-21 B-15 92 545 80 28 45 A'-22 B-16 94 560 85 23 46 A'-24 B-17 90 565 87 18 47 A'-25 B-18 92 560 81 24 48 A'-26 B-19 90 540 80 29 49 A'-27 B-20 90 550 81 24 __________________________________________________________________________
TABLE 12 ______________________________________ Methine Dye (C): ##STR233## Example Resin (A') Resin (B) ______________________________________ 50 A'-4 B-3 51 A'-5 B-4 52 A'-6 B-5 53 A'-8 B-7 54 A'-11 B-8 55 A'-13 B-8 56 A'-15 B-11 57 A'-17 B-11 58 A'-18 B-14 59 A'-19 B-16 60 A'-20 B-2 61 A'-21 B-6 ______________________________________
TABLE 13 ______________________________________ Exam- E.sub.1/10 Printing ple Resin Resin V.sub.10 D.R.R. (lux · Durability No. (A') (B) (-V) (%) sec) (sheets) ______________________________________ 62 A'-1 B-1 580 90 10.3 8000 63 A'-2 B-6 640 95 8.9 8000 64 A'-11 B-9 550 88 11.6 8000 65 A'-24 B-15 610 94 9.2 8000 ______________________________________
TABLE 14 ______________________________________ Example Resin (A') Resin (B) ______________________________________ 66 A'-1 B-2 67 A'-8 B-4 68 A'-12 B-5 69 A'-14 B-7 70 A'-16 B-10 71 A'-17 B-13 72 A'-21 B-15 73 A'-23 B-20 ______________________________________
Claims (6)
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
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JP2-33955 | 1990-02-16 | ||
JP3395590A JPH03238463A (en) | 1990-02-16 | 1990-02-16 | Electrophotographic sensitive body |
JP11853290A JP2670884B2 (en) | 1990-05-10 | 1990-05-10 | Electrophotographic photoreceptor |
JP2-118532 | 1990-05-10 |
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US5206104A true US5206104A (en) | 1993-04-27 |
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US07/655,608 Expired - Lifetime US5206104A (en) | 1990-02-16 | 1991-02-15 | Electrophotographic light-sensitive material |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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US6509133B1 (en) * | 1999-03-25 | 2003-01-21 | Dainippon Ink And Chemicals, Inc. | Lithographic printing plate and image forming method |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4925765A (en) * | 1988-12-23 | 1990-05-15 | E. I. Du Pont De Nemours And Company | Negative solid block toner |
US5009975A (en) * | 1988-10-04 | 1991-04-23 | Fuji Photo Film Co., Ltd. | Electrophotographic photoreceptor |
US5021311A (en) * | 1988-09-02 | 1991-06-04 | Fuji Photo Film Co., Ltd. | Electrophotographic photoreceptor |
-
1991
- 1991-02-15 US US07/655,608 patent/US5206104A/en not_active Expired - Lifetime
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5021311A (en) * | 1988-09-02 | 1991-06-04 | Fuji Photo Film Co., Ltd. | Electrophotographic photoreceptor |
US5009975A (en) * | 1988-10-04 | 1991-04-23 | Fuji Photo Film Co., Ltd. | Electrophotographic photoreceptor |
US4925765A (en) * | 1988-12-23 | 1990-05-15 | E. I. Du Pont De Nemours And Company | Negative solid block toner |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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US6509133B1 (en) * | 1999-03-25 | 2003-01-21 | Dainippon Ink And Chemicals, Inc. | Lithographic printing plate and image forming method |
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